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Publication numberCN1631890 A
Publication typeApplication
Application numberCN 200410011333
Publication date29 Jun 2005
Filing date10 Dec 2004
Priority date10 Dec 2004
Also published asCN100361994C
Publication number200410011333.0, CN 1631890 A, CN 1631890A, CN 200410011333, CN-A-1631890, CN1631890 A, CN1631890A, CN200410011333, CN200410011333.0
Inventors王悦, 霍成, 郭建华
Applicant吉林大学
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Tetraphenyl porphyrin derivative and its application in organic electroluminescent device
CN 1631890 A
Abstract
The invention relates to a (1) or (2) and its application in preparation of organic EL device. M is Zn or Pt; three substituent group or R1, R2, R3 are different or the same and at least one of them is alkoxy substituent carbazole derivative shown as (3); R10 and R11 are different or the same, as alkyl of C1-4 (n=4-12); the other two substituent group is H and alkoxy and alkyl (C1-C4) or alkoxy substituent carbazole derivative shown as (3). The device made by the invention has high efficiency of EL, outstanding solubility and filmibility, easy to be mixed with polymer, benefiting for research to EL device, can be used to prepare red luminous, with simple technique, benefit for industrialized batch production .
Claims(4)  translated from Chinese
1.通式(1)或(2)所示的以四苯基卟啉为基本结构骨架的四苯基卟啉衍生物, 1. The general formula (1) or (2) shown in tetraphenylporphyrin skeleton as a basic structure tetraphenylporphyrin derivative, M为Zn或Pt,R1、R2、R3三个取代基团相同或不同,其中至少有一个取代基团为式(3)所示的烷氧基取代咔唑衍生物,R10和R11相同或不同,是H或者是C1-4的烷基,n=4-12;其余两个取代基团为H、C1-C4的烷氧基、烷基或式(3)所示的烷氧基取代咔唑衍生物。 M is Zn or Pt, R1, R2, R3 three substituents the same or different groups, in which at least one substituent group of the formula (3) alkoxy-substituted carbazole derivatives, R10 and R11 are the same or different , is H or a C1-4 alkyl group, n = 4-12; the remaining two substituents is H, C1-C4 alkoxy, alkyl or formula (3) alkoxy substituted carbazole derivatives.
2.权利要求1所述的四苯基卟啉衍生物在制备有机电致发光器件方面的应用。 Tetraphenylporphyrin derivative according to claim 1 for the preparation of organic electroluminescent light emitting device application areas.
3.如权利要求2所述的四苯基卟啉衍生物在制备有机电致发光器件方面的应用,其特征在于:电致发光器件带有一个或多个活性层,在这些活性层中至少有一层含有一种或多种本发明所述化合物(1)或(2)。 3. The tetraphenylporphyrin derivative of claim 2, wherein there is applied in the preparation of an organic electroluminescent device aspect, wherein: the electroluminescent device having one or more active layers, at least in these active layers a layer containing one or more compounds of the present invention (1) or (2).
4.如权利要求3所述的四苯基卟啉衍生物在制备有机电致发光器件方面的应用,其特征在于:活性层是一个光发射层和/或一迁移层和/或一电荷注入层。 The tetraphenylporphyrin derivative according to claim 3 in the preparation of organic electroluminescent light emitting device application aspect, wherein: the active layer is a light-emitting layer and / or a transport layer and / or a charge injection layers.
Description  translated from Chinese
四苯基卟啉衍生物及其在有机电致发光器件中的应用 Tetraphenylporphyrin derivatives and their application in organic electroluminescent devices

技术领域 FIELD

本发明涉及一种有机电致发光材料及其应用,具体涉及一种四苯基卟啉衍生物及其作为发光材料在有机电致发光器件中的应用。 The present invention relates to an organic electroluminescent materials and their applications, in particular to a tetraphenylporphyrin derivatives and organic electroluminescent device in the application of electrical and mechanical as a luminescent material.

背景技术 BACKGROUND

有机电致发光现象被发现已有三十多年的时间,1987年以前,由于有机电致发光器件存在的巨大缺陷(开启电压>200V),限制了其应用。 Organic electroluminescence phenomenon was discovered over 30 years of time, before 1987, due to the presence of organic electroluminescent devices huge deficiencies (turn-on voltage> 200V), limiting its application. 近十年以来由于材料及器件工艺的不断突破,使有机电致发光已达到或接近实用化阶段。 For nearly a decade as a result of material and device technology continues to break, so that the organic electroluminescent have reached or approached the practical stage.

1965年Gurnee等首次发表了关于有机电致发光器件的专利(USPat.No.3,172,862,3,173,050)。 Gurnee first published in 1965 and so on patented organic electroluminescent devices (USPat.No.3,172,862,3,173,050). 1973年Dresner也发表了有机电致发光器件方面的专利(USPat.No.3,170,167)。 1973 Dresner also made organic electroluminescent device aspects of the patent (USPat.No.3,170,167). 在这些发明中多芳环有机化合物如蒽、四并苯、五并苯等被用于有机电致发光材料。 In these inventions polyaromatic organic compounds such as anthracene, four and benzene, and benzene and the like are used for five organic electroluminescent material. 早期的器件主要结构特征为单层结构,有机发光层的厚度大于1mm,器件的开启电压在200v以上。 The main structural features of the early devices are single-layer structure, the thickness of the organic light emitting layer is greater than 1mm, the threshold voltage of the device at 200v above.

80年代美国柯达公司公司的气味等首先发现超薄多层器件结构,使器件的开启电压大大降低(USPat.No.4,356,429)。 1980s Kodak Company's smell first discovered thin multilayer device structure, the threshold voltage of the device significantly reduced (USPat.No.4,356,429). 其器件的基本特征是以导电玻璃为衬底,先蒸镀上一层空穴注入层(100nm),同时也是传输层,然后旋涂上一层有机电子传输层,同时也是电致发光层,最后镀上一层金属作为负极,该器件开启电压为20v,亮度为5cd/m2。 The basic characteristics of the device based on its conductive glass substrate, the first layer deposited on the hole injection layer (100nm), but also the transport layer, and then spin-coated with an organic electron transport layer, an electroluminescent layer is also, Finally, coated with a layer of metal as the anode, the device turn-on voltage of 20v, brightness 5cd / m2. 之后柯达公司公司VanSlyke等采用芳香多胺为空穴传输层进行器件制备,使器件性能大大提高,亮度可达340cd/m2。 After Kodak Company VanSlyke and other aromatic polyamines were prepared using the device as a hole transport layer, so that the device performance is greatly improved, the brightness of up to 340cd / m2.

美国柯达公司公司的VanSlyke和气味首先发现Alq3(8-羟基喹啉铝)具有良好的电致发光性能以后,人们相继用8-羟基喹啉及其衍生物与Al3+、Zn2+、Ga3+、Be2+等合成出了一系列电致发光材料,这些材料大部分发黄绿光,有些发蓝光(见USPat.No.4,720,432;USPat.No.4,539,507;CWTang,SAVanSlyke,Appl.Phys.1987,51,913;USPat.No.5,151,629;Hamada,Jpn.J.Appl.Phys.,部分2.,1992,32,L 514;Matsumura,Jpn.J.Appl.Phys.,1996,35,5357;洞穴,J.Appys.,1996,79,7991)。 Eastman Kodak Company's VanSlyke and smell first discovered Alq3 (8- hydroxyquinoline aluminum) has a good performance after electroluminescent, people have been using 8-hydroxyquinoline and its derivatives and Al3 +, Zn2 +, Ga3 +, Be2 + synthetic a series of electroluminescent material, most of these materials yellow green hair, some hair blue (see USPat.No.4,720,432; USPat.No.4,539,507; CWTang, SAVanSlyke, Appl.Phys.1987,51,913; USPat.No .5,151,629; Hamada, Jpn.J.Appl.Phys, part 2., 1992,32, L 514;. Matsumura, Jpn.J.Appl.Phys, 1996,35,5357;. cave, J.Appys, 1996. , 79,7991). 日本Sanyo公司的Sano等在USPat.5,432,014中用西弗碱-锌配合物作为发光层制备了蓝光器件。 Japan's Sanyo Sano et USPat.5,432,014 base with Sev - zinc complexes as luminescent layer Blu-ray devices prepared. 值得注意的是日本Sanyo公司的Hamada等合成出10-羟基苯并喹啉化合物,其电致发光性能超过了Alq3(Hamadadeng Chem.lett.,1993,950)。 It is noteworthy that Japan's Sanyo Hamada and other synthesized 10- hydroxy quinoline compound electroluminescent performance over the Alq3 (Hamadadeng Chem.lett., 1993,950).

由于一些性能优良的电致发光材料的发现和器件结构的不断优化,使有机电致发光已取得了一些突破性进展。 Due to continuous optimization and device structures found some excellent performance of electroluminescent material, so that the organic electroluminescent have made some breakthrough. (见USPat.No.5,151,629;5,150,006;5,141,671;5,073,446;5,061,569;5,059,862;5,059,861;5,047,687;4,950,950;5,104,740;5,227,252;5,256,945;5,069,957;5,122,711;5,554,450;5,683,823;5,593,788;5,645,948;5,451,343;5,623,080;5,395,862)。 (See USPat.No.5,151,629; 5,150,006; 5,141,671; 5,073,446; 5,061,569; 5,059,862; 5,059,861; 5,047,687; 4,950,950; 5,104,740; 5,227,252; 5,256,945; 5,069,957; 5,122,711; 5,554,450; 5,683,823; 5,593,788; 5,645,948; 5,451,343; 5,623,080; 5,395,862).

卟啉化合物作为发光材料被运用到电致发光领域里主要是从1998年开始的。 Porphyrin compound as a luminescent material is applied to the electroluminescent areas mainly from the beginning of 1998. 1998年美国普林斯顿大学的研究小组采用磷光材料八乙基卟啉铂做为掺杂材料,电子传输材料Alq3作为主体材料制备了红光发射器件(见USPat.No.6,303,238;SRForrest,性质,1998,395,151),最大外量子效率为4%。 1998 Princeton University research team of the United States using a phosphorescent material octaethylporphyrin platinum as a dopant material, the electron transport material Alq3 red light-emitting devices as the host material was prepared (see USPat.No.6,303,238; SRForrest, nature, 1998, 395,151), the maximum external quantum efficiency of 4%. 从此开辟了磷光卟啉化合物在电致发光方面应用的先河。 Since then opened a phosphorescent porphyrin compounds in electroluminescent application of precedent. 1999年美国南加利福尼亚大学和普林斯顿大学的科研小组又开发了两种不同取代基团的卟啉铂化合物PtDPP、PtOX,制备了红光发射器件(见USPat.No.6,413,656;SRForrest,Chem.Mater,1999,11,3709)。 1999 American University of Southern California and a research team at Princeton University has developed two different substituents platinum porphyrin compound PtDPP, PtOX, red light-emitting devices fabricated (see USPat.No.6,413,656; SRForrest, Chem.Mater, 1999,11,3709). 但是它们的外量子效率均比较低,且稳定性较差,不具有载流子传输性能。 But their external quantum efficiency were lower and less stable, having no carrier-transporting properties. 因此寻找效率高、稳定性好、同时具有载流子传输性能,能够实现高效电致发光的材料是一个迫切需要解决的问题。 So look for high efficiency, good stability, while having a carrier transmission performance, to achieve efficient electroluminescent material is an urgent need to address the problem.

发明内容 SUMMARY

本发明的目的是提供一类可以在较宽浓度范围内实现发光效率高、稳定性好、具有载流子传输性能的有机电致发光材料,以及该材料在有机电致发光器件中的应用。 Object of the present invention is to provide a class can achieve high luminous efficiency, good stability, having a carrier transport property organic electroluminescent material, and the material in the organic electroluminescent device of application in a wide concentration range.

经研究发现,四苯基卟啉衍生物具有优良的电致发光特性。 The study found that four porphyrin derivatives have excellent electroluminescent properties. 本发明的对象是结构式如(1) Object of the invention is as structural formula (1) 和(2)所示的一类化合物。 And a class of compounds represented by formula (2).

通式(1)和(2)代表以四苯基卟啉为基本结构骨架的四苯基卟啉衍生物,其中M为锌(Zn)或Pt;R1、R2、R3三个取代基团可以相同或不同,其中至少有一个取代基团为式(3)所示的烷氧基取代咔唑衍生物(其中R10和R11可以相同或不同,可以是H或者是C1-4的烷基,n=4-12),其余两个取代基团为H、C1-C4的烷氧基、烷基或式(3)所示的烷氧基取代咔唑衍生物。 Formula (1) and (2) representative tetraphenylporphyrin skeleton as a basic structure tetraphenylporphyrin derivative, wherein M is zinc (Zn) or Pt; R1, R2, R3 three substituent groups may be are the same or different, wherein at least one substituent group is of formula (3) below alkoxy substituted carbazole derivatives (wherein R10 and R11 may be the same or different and are H or a C1-4 alkyl group, n = 4-12), the remaining two substituent groups are H, C1-C4 alkoxy group, an alkyl group or (3) alkoxy-substituted carbazole derivatives as shown.

本发明式(1)和(2)为新四苯基卟啉衍生物。 The present invention is of formula (1) and (2) for the new tetraphenylporphyrin derivative. 本发明式(1)和(2)的化合物适用于制备高性能的有机电致发光器件。 The compounds of the invention of formula (1) and (2) are suitable for preparing high-performance organic electroluminescent device. 应用本发明材料制备的器件优点是电致发光效率高,溶解性、成膜性好,易于同聚合物共混从而进行器件的研究,使器件工艺变得简单,有利于器件批量工业化生产。 Material of the present invention is applied to a device for preparing the advantage of high dielectric electroluminescent efficiency, solubility, good film, with the polymer blend thus easy to carry out studies of the device, the device process becomes simple, allowing the device to batch industrial production.

首先制备烷氧基取代咔唑衍生物: First preparing alkoxy substituted carbazole derivatives: 为制备四苯基卟啉衍生物按如下反应模式1进行:反应模式1:1-1,当R1、R2、R3三个取代基团有一个为烷氧基取代咔唑衍生物时,制备四苯基卟啉衍生物的制备模式如下: To prepare the tetraphenylporphyrin derivative according to the following reaction pattern 1: Reaction Mode 1: 1-1, when R1, R2, R3 three substituents for the alkoxy group has a substituted carbazole derivatives, the preparation of four preparing mode porphyrin derivatives as follows:

模式1-2:当R1、R2、R3三个取代基团有二个为烷氧基取代咔唑衍生物时,制备四苯基卟啉衍生物的制备模式如下: Mode 1-2: When R1, R2, R3 three substituents for the alkoxy group has two substituted carbazole derivatives, preparation mode tetraphenyl porphyrin derivative was prepared as follows:

模式1-3:当R1、R2、R3三个取代基团都为烷氧基取代咔唑衍生物时,制备四苯基卟啉衍生物的制备模式如下: Mode 1-3: When R1, R2, R3 three substituent groups are alkoxy-substituted carbazole derivatives, preparation mode tetraphenyl porphyrin derivative was prepared as follows:

由于按反应模式1(1-1、1-2、1-3)所合成的四苯基卟啉衍生物具有较大C4-C12的N-咔唑取代烷氧基团,对卟啉核心起到了空间隔离的功能,因此减弱了发光时的浓度淬灭效应,同时增加了材料的溶解性和成膜性,有利于同聚合物共混从而进行器件研究。 Since the mode 1 in Reaction (1-1,1-2,1-3) synthesized tetraphenylporphyrin derivative having the larger C4-C12 alkoxy substituted N- carbazole group, a porphyrin core pairs at the spatial segregation of functions, thus weakening the concentration quenching effect is illuminated, while increasing the solubility and film-forming materials, help with the study of polymer blends and thus make the device.

由于咔唑的荧光发射峰与卟啉吸收带有很大的重叠,咔唑基团上产生的激发态能量能够传递到中心卟啉核上,从而导致更好的红光发射;同时咔唑具有良好的载流子传输性能,因此以这些材料制备的器件具有更高的电致发光效率。 Because carbazole porphyrin fluorescence emission peak absorption with a lot of overlap, excited state energy generated on carbazole groups can be passed to the central porphyrin core, leading to a better red emission; at the same time having carbazole good carrier transport properties, and therefore the device for preparing these materials have higher electroluminescence efficiency.

反应模式1采用的原料为咔唑或取代咔唑,C4-C12的双溴代烷,吡咯,取代苯甲醛。 The reaction raw material used for mode 1 or a substituted carbazole carbazole, C4-C12 double bromo, pyrrole, a substituted benzaldehyde. 前两种原料在N,N-二甲基甲酰胺溶液中(在NaH存在条件下)回流反应生成化合物(3),后两种原料在N,N-二甲基甲酰胺溶液中回流条件下反应生成化合物(A)、(B)、(D),化合物(B)、(D)在甲醇和三溴化硼混合溶液中回流反应获得化合物(C)、(E),化合物(C)、(E)在N,N-二甲基甲酰胺、三乙胺、化合物(3)混合溶液中反应获得目标化合物(1),化合物(1)在丙酸、醋酸锌混合溶液中加热反应或在乙腈、二氯化铂混合溶液中加热反应获得目标化合物(2)。 The first two materials in N, N- dimethylformamide solution (in the presence of NaH) was refluxed for reaction of the compound (3), the latter two materials in N, N- dimethylformamide under reflux conditions for solution reaction of the compound (A), (B), (D), the compound (B), (D) and boron tribromide in methanol mixed solution was refluxed for reaction to obtain the compound (C), (E), the compound (C), (E) in N, N- dimethylformamide, triethylamine, the compound (3) obtained by reacting a mixed solution of the target compound (1), the compound (1) in propionic acid, zinc acetate or heating the reaction mixture solution in acetonitrile, platinum dichloride heating the reaction mixture solution to obtain the title compound (2).

本发明的化合物可以作为电致发光材料用于制备电致发光器件,尤其可用于电致发光器件的活性层。 Compounds of the invention can be used as electroluminescent material for the preparation of an electroluminescent device, particularly useful in an electroluminescent device of the active layer. 所谓活性层就是在一定驱动电压下能发光或具有电荷注入、传输性能的有机薄膜层。 The so-called active layer is under a certain driving voltage capable of emitting light having an organic thin film layer or charge injection, transmission performance. 因此本发明的对象也是本发明的式(1)和(2)化合物作为电致发光材料的应用以及含有式(1)和(2)化合物的混合物作为电致发光材料的应用。 (2) Compound (1) and therefore an object of the present invention are also the present invention as electroluminescent material, and comprising the application of the formula (1) and mixture (2) compounds as electroluminescent material applications.

通过器件电致发光光谱、亮度、电流/电压特性分析方法测试材料及器件性能,应用本发明式(1)和(2)化合物的电致发光器件其特性如下:开启电压4.5V左右,最大亮度达到240cd/m2,最大外量子效率达5.68%。 Photoluminescence spectra through the device power, brightness, electrical current / voltage characteristic analysis methods to test materials and device performance, (2) application of the present invention is a compound of formula (1) and the electroluminescent device whose characteristics are as follows: turn around voltage 4.5V, the maximum brightness reach 240cd / m2, the maximum external quantum efficiency of 5.68%. 由此可见,本发明式(1)和(2)的化合物合成方法简单、提纯方便、应用于电致发光红光材料具有开启电压低、亮度高、发光效率高、稳定性好等特点。 Thus, the invention of formula (1) and (2) the compound synthesis method is simple, easy purification, used in electroluminescent red light materials with low turn-on voltage, high brightness, high luminous efficiency, good stability.

附图说明 Brief Description

图1:应用本发明所述有机材料的电致发光器件结构示意图。 Figure 1: Application of the present invention is the organic electroluminescent device material is a schematic structural view.

现结合附图来说明本发明式(1)和(2)化合物在电致发光器件中的应用。 Now be described with reference to (2) compounds of the present invention of formula (1) and the electroluminescent device application. 本发明的对象可用于制备带有一个或多个活性层的电致发光器件,而且这些活性层中至少一层含有一种或多种本发明的化合物。 Object of the present invention can be used to prepare one or more electrically active layers having the electroluminescent device, and at least one of these active layers comprises one or more compounds of the present invention. 活性层可以是一个光发射层和/或一迁移层和/或一电荷注射层。 The active layer may be a light-emitting layer and / or a transport layer and / or a charge injection layer. 此类发光器件的基本结构如图1所示,该图为一多层结构的电致发光器件,其由附着在透光玻璃1上的ITO(氧化铟锡)导电层(正极)2和金属(Al,Mg:Ag合金,Ca,Na,K)层(负极)7以及夹在两极之间的两个载流子注入层(空穴注入层3和电子注入层6)和两个活性层构成,这两个活性层分别由空穴传输材料(如NPB)4和发光材料同时也是电子传输材料5构成,5中所用材料为本发明所述的有机电致发光材料,或包含本发明所述的有机电致发光材料。 The basic structure of such a light emitting device shown in Figure 1, the picture shows an electroluminescent device a multilayer structure, consisting of a light-transmissive glass adhered on the ITO (indium tin oxide) conductive layer (positive electrode) 2 and the metal (Al, Mg: Ag alloy, Ca, Na, K) layer (anode) 7 and sandwiched between the two poles of the carrier injection layer (hole injection layer 3 and the electron injecting layer 6) and two active layers configuration, the two active layers are a hole transporting material (e.g. NPB) 4 and a light emitting material but also electron-transporting material constituting 5, 5 in the materials according to the present invention, organic electroluminescent materials, or the present invention comprising described organic electroluminescent material. 空穴和电子分别从正负两极注入,分别在空穴传输层和电子传输层(也是发光层)中传输,在两层的界面附近区域电子和空穴复合,并产生激子,激子通过辐射跃迁回到基态,就有光发出。 Holes and electrons are injected from the positive and negative poles, respectively, in the hole-transporting layer and an electron transport layer (also a light emitting layer) in the transmission, and the vicinity of the electron-hole recombination at the interface of the two layers, and generates excitons, exciton by radiative transition to the ground state, there is the light emitted.

这种发射光的颜色可通过更换作为发光层应用的化合物加以改变,应用本发明的材料可以制备红色发光器件。 The color of the emitted light can be used as the compound by replacing the light emitting layer application to be changed, the application material of the present invention is a red light emitting device can be prepared. 在电致发光层和阴极之间可附加装入一层电子注射层和/或电子迁移层来提高器件性能。 The electroluminescent layer may be additionally charged electron injection layer and / or electron transporting layer between the light emitting layer and the cathode to improve device performance.

这些电致发光装置可应用作自身发光的指示元件如信号灯、字母数字显示器、指示牌、光电偶合器上、各种平板显示器(手机、数码摄像机、数码照像机、掌上电脑等的显示屏)中的应用。 The electroluminescent device can be used as an indication of self-luminous elements such as the lights, alphanumeric displays, signs, optical coupler, a variety of flat panel displays (mobile phones, digital cameras, digital cameras, handheld computers and other display) Application.

具体实施方式 DETAILED DESCRIPTION

下面通过实例来进一步阐明本发明化合物的制备及应用,而不是要用这些实例来限制本发明,所有原料均可以从商业渠道获得。 The following examples further illustrated by preparation and application of the compounds of the present invention, and not to limit the use of these examples of the present invention, all raw materials are available from commercial sources.

实例1:化合物1-1-01的合成用150毫升N,N-二甲基甲酰胺作溶剂,加入化合物氢化钠3.0克,咔唑10克和1,4-二溴丁烷20.0克,回流反应6小时。 Example 1: Synthesis of Compound 1-1-01 with 150 ml N, N- dimethylformamide as solvent, was added 3.0 g of sodium hydride compounds, carbazole and 10 g of 1,4-dibromobutane 20.0 g, reflux The reaction for 6 hours. 冷却,加入50毫升甲醇充分搅拌后过滤,收集的滤液浓缩蒸干,粗产物用环己烷为洗脱剂三氧化二铝为固定相柱层析,即得产物N-(4-溴丁基)咔唑8.2克。 After cooling, 50 ml of methanol was stirred sufficiently collected by filtration and filtrate was concentrated to dryness, the crude product was cyclohexane as eluant to aluminum oxide as the stationary phase column chromatography to give the product N- (4- bromobutyl ) carbazole 8.2 g. 产率45.4%。 Yield of 45.4%.

将化合物3-甲氧基-4-羟基苯甲醛10.0克,吡咯4.4克和N,N-二甲基甲酰胺600毫升加热回流2小时,冷却静止,加入200毫升蒸馏水,过滤,将粗产物用二氯甲烷为洗脱剂、三氧化二铝为固定相柱层析,即得产物四-(3-甲氧基-4-羟基)苯基卟啉3.5克。 The compound 3-methoxy-4-hydroxybenzaldehyde 10.0 g, pyrrole 4.4 g and N, N- dimethylformamide 600 ml was heated at reflux for 2 hours, cooled stationary, was added 200 ml of distilled water, filtered and the crude product was dichloromethane as eluant, aluminum oxide as the stationary phase column chromatography to obtain the product four - (3-methoxy-4-hydroxy) phenyl porphyrin 3.5 g. 产率26.7%。 Yield of 26.7%.

将化合物四-(3-甲氧基-4-羟基)苯基卟啉1.0克加入N-(4-溴丁基)咔唑3.0克,三乙胺2.0毫升,N,N-二甲基甲酰胺600毫升,加热搅拌反应12小时。 Compound four - (3-methoxy-4-hydroxy) phenyl porphyrin 1.0 g was added N- (4- bromobutyl) carbazole 3.0 g, 2.0 ml of triethylamine, N, N- dimethylformamide amide 600 ml, was heated with stirring for 12 hours. 产物用蒸馏水和二氯甲烷萃取,二氯甲烷萃取液浓缩,用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析即得产物四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉1.9克。 The product was extracted with distilled water and methylene chloride, methylene chloride extract was concentrated, diluted with methylene chloride as eluant alumina as the stationary phase column chromatography to obtain the product of four - [3-methoxy -4- (N - carbazole) butoxy] porphyrin 1.9 g. 产率:90.1%。 Yield: 90.1%. 质谱分子离子峰:1683。 Mass molecular ion peak: 1683. 元素分析按化学式C112H98N8O8计算:C:79.9%;H:5.9%;N:6.6%;O:7.6%实验值:C:79.8%;H:5.8%;N:6.7%;O:7.4%。 Elemental analysis is calculated according to the formula C112H98N8O8: C: 79.9%; H: 5.9%; N: 6.6%; O: 7.6% Found: C: 79.8%; H: 5.8%; N: 6.7%; O: 7.4%.

四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉1-1-01实例2:化合物1-1-02的合成化合物1-1-02的合成与实例1一样。 Four - [3-methoxy -4- (N- carbazole) butoxy] phenyl porphyrin 1-1-01 Example 2: Synthesis of compound 1-1-02 and 1-1-02 Synthesis the same as in Example 1. 只是用的是1,5-二溴戊烷代替1,4-二溴丁烷。 Except that 1,5-dibromopentane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)戊氧基]苯基卟啉。 The product four - [3-methoxy -4- (N- carbazole) pentyloxy] phenyl porphyrin. 质谱分子离子峰:1739。 Mass molecular ion peak: 1739. 元素分析按化学式C116H106N8O8计算:C:80.0%;H:6.1%;N:6.4%;O:7.4%;实验值:C:79.8%;H:6.2%;N:6.5%;O:7.5%。 Elemental analysis by chemical formula C116H106N8O8 calculation: C: 80.0%; H: 6.1%; N: 6.4%; O: 7.4%; Found: C: 79.8%; H: 6.2%; N: 6.5%; O: 7.5%.

实例3:化合物1-1-03的合成化合物1-1-03的合成与实例1一样。 Example 3: Synthesis of Compound 1-1-03 1-1-03 Synthesis Example 1 of the same. 只是用的是1,6-二溴己烷代替1,4-二溴丁烷。 Except that 1,6-dibromohexane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)己氧基]苯基卟啉。 The product four - [3-methoxy -4- (N- carbazole) hexyloxy] phenyl porphyrin. 质谱分子离子峰:1795。 Mass molecular ion peak: 1795. 元素分析按化学式C120H114N8O8计算:C:80.0%;H:6.4%;N:6.2%;O:7.1%;实验值:C:80.2%;H:6.3%;N:6.1%;O:7.2%。 Elemental analysis by chemical formula C120H114N8O8 calculation: C: 80.0%; H: 6.4%; N: 6.2%; O: 7.1%; Found: C: 80.2%; H: 6.3%; N: 6.1%; O: 7.2%.

实例4:化合物1-1-04的合成化合物1-1-04的合成与实例1一样。 Example 4: Synthesis of Compound 1-1-04 compound 1-1-04 of Synthesis Example 1 as. 只是用的是1,7-二溴庚烷代替1,4-二溴丁烷。 Except that 1,7-dibromoheptane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)庚氧基]苯基卟啉。 The product four - [3-methoxy -4- (N- carbazole) heptyloxy] phenyl porphyrin. 质谱分子离子峰:1851。 Mass molecular ion peak: 1851. 元素分析按化学式C124H122N8O8计算:C:80.4%;H:6.6%;N:6.1%;O:6.9%;实验值:C:80.2%;H:6.5%;N:6.0%;O:7.0%。 Elemental analysis by chemical formula C124H122N8O8 calculation: C: 80.4%; H: 6.6%; N: 6.1%; O: 6.9%; Found: C: 80.2%; H: 6.5%; N: 6.0%; O: 7.0%.

实例5:化合物1-1-05的合成化合物1-1-05的合成与实例1一样。 Example 5: Synthesis of Compound Compound Synthesis Example 1-1-05 1-1-05 1 same. 只是用的是1,8-二溴辛烷代替1,4-二溴丁烷。 Except that 1,8-dibromo-octane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)辛氧基]苯基卟啉。 The product four - [3-methoxy -4- (N- carbazole) octyloxy] phenyl porphyrin. 质谱分子离子峰:1907。 Mass molecular ion peak: 1907. 元素分析按化学式C128H130N8O8计算:C:80.6%;H:6.9%;N:5.9%;o:6.7%;实验值:C:80.9%;H:6.8%;N:6.1%;O:7.0%。 Elemental analysis by chemical formula C128H130N8O8 calculation: C: 80.6%; H: 6.9%; N: 5.9%; o: 6.7%; Found: C: 80.9%; H: 6.8%; N: 6.1%; O: 7.0%.

实例6:化合物1-1-06的合成化合物1-1-06的合成与实例1一样。 Example 6: Synthesis of Compound 1-1-06 compound 1-1-06 of Synthesis Example 1 as. 只是用的是1,9-二溴壬烷代替1,4-二溴丁烷。 Except that 1,9-dibromo-nonane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)壬氧基]苯基卟啉。 The product four - [3-methoxy -4- (N- carbazole) nonyl oxy] phenyl porphyrin. 质谱分子离子峰:1963。 Mass molecular ion peak: 1963. 元素分析按化学式C132H138N8O8计算:C:80.7%;H:7.1%;N:5.7%;O:6.5%;实验值:C:80.8%;H:6.9%;N:6.0%;O:6.4%。 Elemental analysis by chemical formula C132H138N8O8 calculation: C: 80.7%; H: 7.1%; N: 5.7%; O: 6.5%; Found: C: 80.8%; H: 6.9%; N: 6.0%; O: 6.4%.

实例7:化合物1-1-07的合成化合物1-1-07的合成与实例1一样。 Example 7: Synthesis of Compound 1-1-07 1-1-07 Synthesis Example 1 of the same. 只是用的是1,10-二溴癸烷代替1,4-二溴丁烷。 Except that the 1,10-dibromodecane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)癸氧基]苯基卟啉。 The product four - [3-methoxy -4- (N- carbazole) decyloxy] phenyl porphyrin. 质谱分子离子峰:2019。 Mass molecular ion peak: 2019. 元素分析按化学式C136H146N8O8计算:C:80.8%;H:7.3%;N:5.6%;O:6.3%;实验值:C:80.5%;H:7.4%;N:5.8%;O:6.2%。 Elemental analysis by chemical formula C136H146N8O8 calculation: C: 80.8%; H: 7.3%; N: 5.6%; O: 6.3%; Found: C: 80.5%; H: 7.4%; N: 5.8%; O: 6.2%.

实例8:化合物1-1-08的合成化合物1-1-08的合成与实例1一样。 Example 8: Synthesis of Compound 1-1-08 1-1-08 synthesis of Example 1 the same. 只是用的是1,11-二溴十一烷代替1,4-二溴丁烷。 Except that 1,11-dibromo-undecane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)十一烷氧基]苯基卟啉。 The product of four - [3-methoxy -4- (N- carbazolyl) undecyloxyphenyl] porphyrin. 质谱分子离子峰:2075。 Mass molecular ion peak: 2075. 元素分析按化学式C140H154N8O8计算:C:81.0%;H:7.5%;N:5.4%;O:6.2%;实验值:C:81.2%;H:7.3%;N:5.1%;O:6.5%。 Elemental analysis by chemical formula C140H154N8O8 calculation: C: 81.0%; H: 7.5%; N: 5.4%; O: 6.2%; Found: C: 81.2%; H: 7.3%; N: 5.1%; O: 6.5%.

实例9:化合物1-1-09的合成化合物1-1-09的合成与实例1一样。 Example 9: Synthesis of Compound 1-1-09 1-1-09 Synthesis Example 1 of the same. 只是用的是1,12-二溴十二烷代替1,4-二溴丁烷。 Except that the 1,12-dibromo dodecane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)十二烷氧基]苯基卟啉。 The product of four - [3-methoxy -4- (N- carbazolyl) dodecoxy] porphyrin. 质谱分子离子峰:2131。 Mass molecular ion peak: 2131. 元素分析按化学式C144H162N8O8计算:C:81.1%;H:7.7%;N:5.3%;O:6.0%;实验值:C:81.2%;H:7.3%;N:5.1%;O:6.2%。 Elemental analysis by chemical formula C144H162N8O8 calculation: C: 81.1%; H: 7.7%; N: 5.3%; O: 6.0%; Found: C: 81.2%; H: 7.3%; N: 5.1%; O: 6.2%.

实例10:化合物1-1-10的合成化合物1-1-10的合成与实例1一样。 Example 10: Synthesis of Compound 1-1-10 1-1-10 Synthesis Example 1 of the same. 只是用的是3-乙氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-ethoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-乙氧基-4-(N-咔唑)丁氧基]苯基卟啉。 The product four - [3-ethoxy -4- (N- carbazole) butoxy] phenyl porphyrin. 质谱分子离子峰:1739。 Mass molecular ion peak: 1739. 元素分析按化学式C116H106N8O8计算:C:80.0%;H:6.1%;N:6.4%;O:7.4%;实验值:C:79.6%;H:6.2%;N:6.5%;O:7.6%。 Elemental analysis by chemical formula C116H106N8O8 calculation: C: 80.0%; H: 6.1%; N: 6.4%; O: 7.4%; Found: C: 79.6%; H: 6.2%; N: 6.5%; O: 7.6%.

四-[3-乙氧基-4-(N-咔唑)丁氧基]苯基卟啉 四-[3-丙氧基-4-(N-咔唑)丁氧基]苯基卟啉1-1-10 1-1-11 Four - [3-ethoxy -4- (N- carbazole) butoxy] phenyl porphyrin four - [3-propoxy -4- (N- carbazole) butoxy] phenyl porphyrin 1-1-101-1-11

实例11:化合物1-1-11的合成化合物1-1-11的合成与实例1一样。 Example 11: Synthesis of Compound 1-1-11 1-1-11 synthesis of Example 1 the same. 只是用的是3-丙氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-propoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-丙氧基-4-(N-咔唑)丁氧基]苯基卟啉。 The product four - [3-propoxy -4- (N- carbazole) butoxy] phenyl porphyrin. 质谱分子离子峰:1795。 Mass molecular ion peak: 1795. 元素分析按化学式C120H114N8O8计算:C:80.0%;H:6.4%;N:6.2%;O:7.1%;实验值:C:80.3%;H:6.3%;N:6.3%;O:7.2%。 Elemental analysis by chemical formula C120H114N8O8 calculation: C: 80.0%; H: 6.4%; N: 6.2%; O: 7.1%; Found: C: 80.3%; H: 6.3%; N: 6.3%; O: 7.2%.

实例12:化合物1-1-12的合成化合物1-1-12的合成与实例1一样。 Example 12: Synthesis of Compound Compound Synthesis Example 1-1-12 1-1-12 1 same. 只是用的是3-丁氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-butoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-丁氧基-4-(N-咔唑)丁氧基]苯基卟啉。 The product of four - [3-butoxy -4- (N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:1851。 Mass molecular ion peak: 1851. 元素分析按化学式C124H122N8O8计算:C:80.4%;H:6.6%;N:6.1%;O:6.9%;实验值:C:80.6%;H:6.7%;N:6.0%;O:7.1%。 Elemental analysis by chemical formula C124H122N8O8 calculation: C: 80.4%; H: 6.6%; N: 6.1%; O: 6.9%; Found: C: 80.6%; H: 6.7%; N: 6.0%; O: 7.1%.

四-[3-丁氧基-4-(N-咔唑)丁氧基]苯基卟啉 四-[3-叔丁氧基-4-(N-咔唑)丁氧基]苯基卟啉1-1-12 1-1-13实例13:化合物1-1-13的合成化合物1-1-13的合成与实例1一样。 Four - [3-butoxy--4- (N- carbazole) butoxy] phenyl porphyrin four - [3-tert-butoxy -4- (N- carbazole) butoxy] phenyl porphyrin morpholine 1-1-121-1-13 Example 13: Synthesis of Compound 1-1-13 1-1-13 Synthesis Example 1 as. 只是用的是3-叔丁氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-tert-butoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-叔丁氧基-4-(N-咔唑)丁氧基]苯基卟啉。 The product of four - [3-tert-butoxide -4- (N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:1851。 Mass molecular ion peak: 1851. 元素分析按化学式C124H122N8O8计算:C:80.4%;H:6.6%;N:6.1%;O:6.9%;实验值:C:80.3%;H:6.9%;N:6.4%;O:7.1%。 Elemental analysis by chemical formula C124H122N8O8 calculation: C: 80.4%; H: 6.6%; N: 6.1%; O: 6.9%; Found: C: 80.3%; H: 6.9%; N: 6.4%; O: 7.1%.

实例14:化合物1-1-14的合成化合物1-1-14的合成与实例1一样。 Example 14: Synthesis of Compound Compound Synthesis Example 1-1-14 1-1-14 1 same. 只是用的是4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[4-(N-咔唑)丁氧基]苯基卟啉。 The product of four - [4- (N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:1562。 Mass molecular ion peak: 1562. 元素分析按化学式C108H90N8O8计算:C:82.9%;H:5.8%;N:7.2%;O:4.1%;实验值:C:83.3%;H:5.9%;N:7.4%;O:4.2%。 Elemental analysis by chemical formula C108H90N8O8 calculation: C: 82.9%; H: 5.8%; N: 7.2%; O: 4.1%; Found: C: 83.3%; H: 5.9%; N: 7.4%; O: 4.2%.

四-[4-(N-咔唑)丁氧基]苯基卟啉 四-[3-(N-咔唑)丁氧基]苯基卟啉1-1-14 1-1-15 Four - [4- (N- carbazolyl) butoxy] porphyrin four - [3- (N- carbazolyl) butoxy] phenyl porphyrin 1-1-141-1-15

实例15:化合物1-1-15的合成化合物1-1-15的合成与实例1一样。 Example 15: Synthesis of Compound 1-1-15 compound 1-1-15 of Synthesis Example 1 as. 只是用的是3-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-(N-咔唑)丁氧基]苯基卟啉。 The product of four - [3- (N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:1562。 Mass molecular ion peak: 1562. 元素分析按化学式C108H90N8O8计算:C:82.9%;H:5.8%;N:7.2%;O:4.1%;实验值:C:83.1%;H:5.9%;N:7.0%;O:4.2%。 Elemental analysis by chemical formula C108H90N8O8 calculation: C: 82.9%; H: 5.8%; N: 7.2%; O: 4.1%; Found: C: 83.1%; H: 5.9%; N: 7.0%; O: 4.2%.

实例16:化合物1-1-16的合成化合物1-1-16的合成与实例1一样。 Example 16: Synthesis of Compound 1-1-16 1-1-16 Synthesis Example 1 of the same. 只是用的是3.5-二甲氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3.5-dimethoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[2.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉。 The product four - [2.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin. 质谱分子离子峰:1803。 Mass molecular ion peak: 1803. 元素分析按化学式C116H106N8O12计算:C:77.2%;H:5.9%;N:6.2%;O:10.6%;实验值:C:77.3%;H:6.2%;N:6.4%;O:10.1%。 Elemental analysis by chemical formula C116H106N8O12 calculation: C: 77.2%; H: 5.9%; N: 6.2%; O: 10.6%; Found: C: 77.3%; H: 6.2%; N: 6.4%; O: 10.1%.

四-[3.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉 四-[2.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉1-1-16 1-1-17实例17:化合物1-1-17的合成化合物1-1-17的合成与实例1一样。 Four - [3.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin four - [2.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin 1-1-161-1-17 Example 17: Synthesis of Compound Synthesis Example 1-1-17 1-1-17 1 same. 只是用的是2.5-二甲氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 2.5-dimethoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[2.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉。 The product four - [2.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin. 质谱分子离子峰:1803。 Mass molecular ion peak: 1803. 元素分析按化学式C116H106N8O12计算:C:77.2%;H:5.9%;N:6.2%;O:10.6%;实验值:C:77.5%;H:6.0%;N:6.1%;O:10.8%。 Elemental analysis by chemical formula C116H106N8O12 calculation: C: 77.2%; H: 5.9%; N: 6.2%; O: 10.6%; Found: C: 77.5%; H: 6.0%; N: 6.1%; O: 10.8%.

实例18:化合物1-1-18的合成化合物1-1-18的合成与实例1一样。 Example 18: Synthesis of Compound 1-1-18 1-1-18 synthesis of Example 1 the same. 只是用的是3,6-二叔丁基咔唑代替咔唑。 Except that instead of 3,6-di-t-butyl-carbazole carbazole. 产物四-[3-甲氧基-4-(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉。 The product four - [3-methoxy-4- (3,6-di-tert -N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:2131。 Mass molecular ion peak: 2131. 元素分析按化学式C144H162N8O8计算:C:81.1%;H:7.7%;N:5.3%;O:6.0%;实验值:C:81.4%;H:7.5%;N:5.1%;O:5.8%。 Elemental analysis by chemical formula C144H162N8O8 calculation: C: 81.1%; H: 7.7%; N: 5.3%; O: 6.0%; Found: C: 81.4%; H: 7.5%; N: 5.1%; O: 5.8%.

四-[3-甲氧基-4-(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉 四-[3-甲氧基-4-(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉1-1-18 1-1-19 Four - [3-methoxy-4- (3,6-di-t-butyl -N- carbazol-yl) butoxy] phenyl porphyrin four - [3-methoxy-4- (1,3 , 6,8-tetra-t-butyl -N- carbazol-yl) butoxy] phenyl porphyrin 1-1-181-1-19

实例19:化合物1-1-19的合成化合物1-1-19的合成与实例1一样。 Example 19: Synthesis of Compound 1-1-19 1-1-19 Synthesis Example 1 of the same. 只是用的是1,3,6,8-四叔丁基咔唑代替咔唑。 Except that in place of 1,3,6,8-tetra-tert-butyl-carbazole carbazole. 产物四-[3-甲氧基-4-(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉。 The product four - [3-methoxy-4- (1,3,6,8-tetra-tert-butyl -N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:2580。 Mass molecular ion peak: 2580. 元素分析按化学式C176H226N8O8计算:C:81.9%;H:8.8%;N:4.3%;O:5.0%;实验值:C:81.4%;H:8.9%;N:4.1%;O:5.1%。 Elemental analysis by chemical formula C176H226N8O8 calculation: C: 81.9%; H: 8.8%; N: 4.3%; O: 5.0%; Found: C: 81.4%; H: 8.9%; N: 4.1%; O: 5.1%.

实例20:化合物1-2-01的合成用150毫升N,N-二甲基甲酰胺作溶剂,加入化合物氢化钠3.0克,咔唑10克和1,4-二溴丁烷20.0克,回流反应6小时。 Example 20: Synthesis of Compound 1-2-01 with 150 ml N, N- dimethylformamide as solvent, was added 3.0 g of sodium hydride compounds, carbazole and 10 g of 1,4-dibromo-butane 20.0 g, reflux The reaction for 6 hours. 冷却,加入50毫升甲醇充分搅拌后过滤,收集的滤液浓缩蒸干,粗产物用环己烷为洗脱剂三氧化二铝为固定相柱层析,即得产物N-(4-溴丁基)咔唑8.2克。 After cooling, 50 ml of methanol was stirred sufficiently collected by filtration and filtrate was concentrated to dryness, the crude product was cyclohexane as eluant to aluminum oxide as the stationary phase column chromatography to give the product N- (4- bromobutyl ) carbazole 8.2 g. 产率45.4%。 Yield of 45.4%.

将化合物3.5-二甲氧基苯甲醛10.0克,吡咯4.0克和N,N-二甲基甲酰胺600毫升加热回流2小时,冷却静止,加入200毫升蒸馏水,过滤,将粗产物用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析,即得产物四-(3.5-二甲氧基)苯基卟啉2.8克。 The compound 3,5-methoxybenzaldehyde 10.0 g, pyrrole 4.0 g and N, N- dimethylformamide 600 ml was heated at reflux for 2 hours, cooled stationary, was added 200 ml of distilled water, filtered and the crude product with dichloromethane as eluant to aluminum oxide as the stationary phase column chromatography to obtain the product of four - (3,5-dimethoxyphenyl) porphyrin 2.8 g. 产率21.8%。 Yield of 21.8%.

将化合物四-(3.5-二甲氧基)苯基卟啉2.0克加入三溴化硼1毫升,甲醇100毫升,加热回流反应3小时,冷却静止,加入100毫升0.1M稀盐酸,减压蒸馏蒸干溶剂,二氯甲烷洗涤,即得产物四-(3.5-二羟基)苯基卟啉1.7克。 Compound four - (3,5-dimethoxyphenyl) porphyrin 2.0 g of boron tribromide was added 1 ml, 100 ml of methanol was heated under reflux for 3 hours, cooled stationary, dilute hydrochloric acid was added 100 ml 0.1M, vacuum distillation The solvent was evaporated, washed with methylene chloride, that was the product of four - (3,5-hydroxy) phenyl porphyrin 1.7 g. 产率98%。 98% yield.

将化合物四-(3.5-二羟基)苯基卟啉1.0克加入N-(4-溴丁基)咔唑6.0克,三乙胺2.0毫升,N,N-二甲基甲酰胺600毫升,加热搅拌反应12小时。 Compound four - (3,5-dihydroxy) phenyl porphyrin 1.0 g was added N- (4- bromobutyl) carbazole 6.0 g, 2.0 ml of triethylamine, N, N- dimethylformamide, 600 ml, was heated The reaction was stirred for 12 hours. 产物用蒸馏水和二氯甲烷萃取,二氯甲烷萃取液浓缩,用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析即得产物四-[3.5-二(N-咔唑)丁氧基]苯基卟啉2.9克。 The product was extracted with distilled water and methylene chloride, methylene chloride extract was concentrated, diluted with methylene chloride as eluant alumina as the stationary phase column chromatography to obtain the product of four - [3,5-(N- carbazole) butanoate oxy] phenyl porphyrin 2.9 g. 产率:85.6%。 Yield: 85.6%. 质谱分子离子峰:2511。 Mass molecular ion peak: 2511. 元素分析按化学式C172H150N12O8计算:C:82.2%;H:6.0%;N:6.7%;O:5.1%实验值:C:81.8%;H:5.8%;N:6.5%;O:5.4%。 Elemental analysis is calculated according to the formula C172H150N12O8: C: 82.2%; H: 6.0%; N: 6.7%; O: 5.1% Found: C: 81.8%; H: 5.8%; N: 6.5%; O: 5.4%.

四-[3.5-二(N-咔唑)丁氧基]苯基卟啉1-2-01实例21:化合物1-2-02的合成化合物1-2-02的合成与实例20一样。 Four - [3,5-(N- carbazole) butoxy] phenyl porphyrin 1-2-01 Example 21: Synthesis Example Synthesis of Compound 20 Compound 1-2-02 1-2-02 the same. 只是用的是1,5-二溴戊烷代替1,4-二溴丁烷。 Except that 1,5-dibromopentane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)戊氧基]苯基卟啉。 The product four - [3,5-(N- carbazole) pentyloxy] phenyl porphyrin. 质谱分子离子峰:2623。 Mass molecular ion peak: 2623. 元素分析按化学式C180H166N12O8计算:C:82.4%;H:6.4%;N:6.4%;O:4.9%;实验值:C:82.8%;H:6.2%;N:6.5%;O:4.7%。 Elemental analysis by chemical formula C180H166N12O8 calculation: C: 82.4%; H: 6.4%; N: 6.4%; O: 4.9%; Found: C: 82.8%; H: 6.2%; N: 6.5%; O: 4.7%.

实例22:化合物1-2-03的合成化合物1-2-03的合成与实例20一样。 Example 22: Synthesis of Compound 1-2-03 1-2-03 Synthesis Example 20 of the same. 只是用的是1,6-二溴己烷代替1,4-二溴丁烷。 Except that 1,6-dibromohexane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)己氧基]苯基卟啉。 The product four - [3,5-(N- carbazole) hexyloxy] phenyl porphyrin. 质谱分子离子峰:2735。 Mass molecular ion peak: 2735. 元素分析按化学式C188H182N12O8计算:C:82.5%;H:6.7%;N:6.1%;O:4.7%;实验值:C:82.2%;H:6.8%;N:6.3%;O:4.9%。 Elemental analysis by chemical formula C188H182N12O8 calculation: C: 82.5%; H: 6.7%; N: 6.1%; O: 4.7%; Found: C: 82.2%; H: 6.8%; N: 6.3%; O: 4.9%.

实例23:化合物1-2-04的合成化合物1-2-04的合成与实例20一样。 Example 23: Synthesis of Compound 1-2-04 1-2-04 Synthesis Example 20 of the same. 只是用的是1,7-二溴庚烷代替1,4-二溴丁烷。 Except that 1,7-dibromoheptane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)庚氧基]苯基卟啉。 The product four - [3,5-(N- carbazole) heptyloxy] phenyl porphyrin. 质谱分子离子峰:2848。 Mass molecular ion peak: 2848. 元素分析按化学式C196H198N12O8计算:C:82.6%;H:7.0%;N:5.9%;O:4.5%;实验值:C:82.2%;H:6.9%;N:6.0%;O:4.7%。 Elemental analysis by chemical formula C196H198N12O8 calculation: C: 82.6%; H: 7.0%; N: 5.9%; O: 4.5%; Found: C: 82.2%; H: 6.9%; N: 6.0%; O: 4.7%.

实例24:化合物1-2-05的合成化合物1-2-05的合成与实例20一样。 Example 24: Synthesis of Compound 1-2-05 1-2-05 Synthesis Example 20 of the same. 只是用的是1,8-二溴辛烷代替1,4-二溴丁烷。 Except that 1,8-dibromo-octane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)辛氧基]苯基卟啉。 The product of four - [3.5 two (N- carbazolyl) octyloxy] phenyl porphyrin. 质谱分子离子峰:2960。 Mass molecular ion peak: 2960. 元素分析按化学式C204H214N12O8计算:C:82.7%;H:7.3%;N:5.7%;O:4.3%;实验值:C:82.9%;H:7.2%;N:6.0%;O:4.4%。 Elemental analysis by chemical formula C204H214N12O8 calculation: C: 82.7%; H: 7.3%; N: 5.7%; O: 4.3%; Found: C: 82.9%; H: 7.2%; N: 6.0%; O: 4.4%.

实例25:化合物1-2-06的合成化合物1-2-06的合成与实例20一样。 Example 25: Synthesis of Compound 1-2-06 1-2-06 Synthesis Example 20 of the same. 只是用的是1,9-二溴壬烷代替1,4-二溴丁烷。 Except that 1,9-dibromo-nonane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)壬氧基]苯基卟啉。 The product four - [3,5-(N- carbazole) nonyl oxy] phenyl porphyrin. 质谱分子离子峰:3072。 Mass molecular ion peak: 3072. 元素分析按化学式C212H230N12O8计算:C:82.8%;H:7.5%;N:5.5%;O:4.2%;实验值:C:83.1%;H:7.9%;N:5.4%;O:4.4%。 Elemental analysis by chemical formula C212H230N12O8 calculation: C: 82.8%; H: 7.5%; N: 5.5%; O: 4.2%; Found: C: 83.1%; H: 7.9%; N: 5.4%; O: 4.4%.

实例26:化合物1-2-07的合成化合物1-2-07的合成与实例20一样。 Example 26: Synthesis of Compound 1-2-07 1-2-07 Synthesis Example 20 of the same. 只是用的是1,10-二溴癸烷代替1,4-二溴丁烷。 Except that the 1,10-dibromodecane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)癸氧基]苯基卟啉。 The product four - [3,5-(N- carbazole) decyloxy] phenyl porphyrin. 质谱分子离子峰:3184。 Mass molecular ion peak: 3184. 元素分析按化学式C220H246N12O8计算:C:82.9%;H:7.8%;N:5.3%;O:4.0%;实验值:C:82.5%;H:7.9%;N:5.5%;O:4.2%。 Elemental analysis by chemical formula C220H246N12O8 calculation: C: 82.9%; H: 7.8%; N: 5.3%; O: 4.0%; Found: C: 82.5%; H: 7.9%; N: 5.5%; O: 4.2%.

实例27:化合物1-2-08的合成化合物1-2-08的合成与实例20一样。 Example 27: Synthesis of Compound 1-2-08 1-2-08 synthesis of Example 20 the same. 只是用的是1,11-二溴十一烷代替1,4-二溴丁烷。 Except that 1,11-dibromo-undecane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)十一烷氧基]苯基卟啉。 The product four - [3,5-(N- carbazole) undecanoic oxy] phenyl porphyrin. 质谱分子离子峰:3296。 Mass molecular ion peak: 3296. 元素分析按化学式C228H262N12O8计算:C:83.0%;H:8.0%;N:5.1%;O:3.9%;实验值:C:83.2%;H:8.3%;N:5.0%;O:3.7%。 Elemental analysis by chemical formula C228H262N12O8 calculation: C: 83.0%; H: 8.0%; N: 5.1%; O: 3.9%; Found: C: 83.2%; H: 8.3%; N: 5.0%; O: 3.7%.

实例28:化合物1-2-09的合成化合物1-2-09的合成与实例20一样。 Example 28: Synthesis of Compound 1-2-09 1-2-09 Synthesis Example 20 of the same. 只是用的是1,12-二溴十二烷代替1,4-二溴丁烷。 Except that the 1,12-dibromo dodecane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)十二烷氧基]苯基卟啉。 The product four - [3,5-(N- carbazole) dodecyloxy] porphyrin. 质谱分子离子峰:3408。 Mass molecular ion peak: 3408. 元素分析按化学式C236H278N12O8计算:C:83.1%;H:8.2%;N:4.9%;O:3.8%;实验值:C:83.2%;H:8.3%;N:5.1%;O:4.0%。 Elemental analysis by chemical formula C236H278N12O8 calculation: C: 83.1%; H: 8.2%; N: 4.9%; O: 3.8%; Found: C: 83.2%; H: 8.3%; N: 5.1%; O: 4.0%.

实例29:化合物1-2-10的合成化合物1-2-10的合成与实例20一样。 Example 29: Synthesis of Compound 1-2-10 1-2-10 Synthesis Example 20 of the same. 只是用的是3.4-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 3,4-dimethoxybenzaldehyde in place of 3,5-dimethoxybenzaldehyde. 产物四-[3.4-二(N-咔唑)丁氧基]苯基卟啉。 The product four - [3.4 two (N- carbazole) butoxy] phenyl porphyrin. 质谱分子离子峰:2511。 Mass molecular ion peak: 2511. 元素分析按化学式C172H150N12O8计算:C:82.2%;H:6.0%;N:6.7%;O:5.1%实验值:C:82.4%;H:5.8%;N:6.5%;O:5.2%。 Elemental analysis is calculated according to the formula C172H150N12O8: C: 82.2%; H: 6.0%; N: 6.7%; O: 5.1% Found: C: 82.4%; H: 5.8%; N: 6.5%; O: 5.2%.

四-[3.4-二(N-咔唑)丁氧基]苯基卟啉 四-[2.5-二(N-咔唑)丁氧基]苯基卟啉1-2-10 1-2-11 Four - [3.4-two (N- carbazole) butoxy] phenyl porphyrin four - [2,5-di (N- carbazole) butoxy] phenyl porphyrin 1-2-101-2-11

实例30:化合物1-2-11的合成化合物1-2-11的合成与实例20一样。 Example 30: Synthesis of Compound 1-2-11 1-2-11 synthesis of Example 20 the same. 只是用的是2.5-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2,5-dimethyl-methoxybenzaldehyde instead of 3,5-dimethoxybenzaldehyde. 产物四-[2.5-二(N-咔唑)丁氧基]苯基卟啉。 The product four - [2,5-dimethyl (N- carbazole) butoxy] phenyl porphyrin. 质谱分子离子峰:2511。 Mass molecular ion peak: 2511. 元素分析按化学式C172H150N12O8计算:C:82.2%;H:6.0%;N:6.7%;O:5.1%实验值:C:82.5%;H:5.7%;N:6.5%;O:5.2%。 Elemental analysis is calculated according to the formula C172H150N12O8: C: 82.2%; H: 6.0%; N: 6.7%; O: 5.1% Found: C: 82.5%; H: 5.7%; N: 6.5%; O: 5.2%.

实例31:化合物1-2-12的合成化合物1-2-12的合成与实例20一样。 Example 31: Synthesis of Compound 1-2-12 1-2-12 Synthesis Example 20 of the same. 只是用的是2.4-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2,4-dimethoxybenzaldehyde in place of 3,5-dimethoxybenzaldehyde. 产物四-[2.4-二(N-咔唑)丁氧基]苯基卟啉。 The product four - [2.4-(N- carbazole) butoxy] phenyl porphyrin. 质谱分子离子峰:2511。 Mass molecular ion peak: 2511. 元素分析按化学式C172H150N12O8计算:C:82.2%;H:6.0%;N:6.7%;O:5.1%实验值:C:82.4%;H:5.7%;N:6.9%;O:5.0%。 Elemental analysis is calculated according to the formula C172H150N12O8: C: 82.2%; H: 6.0%; N: 6.7%; O: 5.1% Found: C: 82.4%; H: 5.7%; N: 6.9%; O: 5.0%.

四-[2.4-二(N-咔唑)丁氧基]苯基卟啉 四-[2.6-二(N-咔唑)丁氧基]苯基卟啉1-2-12 1-2-13实例32:化合物1-2-13的合成化合物1-2-13的合成与实例20一样。 Four - [2.4-(N- carbazole) butoxy] phenyl porphyrin four - [2,6-two (N- carbazole) butoxy] phenyl porphyrin 1-2-121-2-13 Example 32: Synthesis of Compound 1-2-13 1-2-13 Synthesis Example 20 of the same. 只是用的是2.6-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2,6-dimethoxybenzaldehyde in place of 3,5-dimethoxybenzaldehyde. 产物四-[2.6-二(N-咔唑)丁氧基]苯基卟啉。 The product four - [2,6-two (N- carbazole) butoxy] phenyl porphyrin. 质谱分子离子峰:2511。 Mass molecular ion peak: 2511. 元素分析按化学式C172H150N12O8计算:C:82.2%;H:6.0%;N:6.7%;O:5.1%实验值:C:82.0%;H:5.7%;N:6.9%;O:5.4%。 Elemental analysis is calculated according to the formula C172H150N12O8: C: 82.2%; H: 6.0%; N: 6.7%; O: 5.1% Found: C: 82.0%; H: 5.7%; N: 6.9%; O: 5.4%.

实例33:化合物1-2-14的合成化合物1-2-14的合成与实例20一样。 Example 33: Synthesis of Compound Compound Synthesis Example 1-2-14 1-2-14 20 of the same. 只是用的是3,6-二叔丁基咔唑代替咔唑。 Except that instead of 3,6-di-t-butyl-carbazole carbazole. 产物四-[3,5-二(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉。 The product four - [3,5-bis (3,6-di-tert--N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:3408。 Mass molecular ion peak: 3408. 元素分析按化学式C236H278N12O8计算:C:83.1%;H:8.2%;N:4.9%;O:3.8%实验值:C:83.0%;H:8.4%;N:4.8%;O:4.0%。 Elemental analysis is calculated according to the formula C236H278N12O8: C: 83.1%; H: 8.2%; N: 4.9%; O: 3.8% Found: C: 83.0%; H: 8.4%; N: 4.8%; O: 4.0%.

四-[3.5-二(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉 四-[3.5-二(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉1-2-14 1-2-15 Four - [3.5-bis (3,6-di-t-butyl -N- carbazol-yl) butoxy] phenyl porphyrin four - [3.5-bis (1,3,6,8-tetra-tert-butyl - N- carbazolyl) butoxy] phenyl porphyrin 1-2-141-2-15

实例34:化合物1-2-15的合成化合物1-2-15的合成与实例20一样。 Example 34: Synthesis of Compound Compound Synthesis Example 1-2-15 1-2-15 20 of the same. 只是用的是1,3,6,8-四叔丁基咔唑代替咔唑。 Except that in place of 1,3,6,8-tetra-tert-butyl-carbazole carbazole. 产物四-[3,5-二(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉。 The product four - [3,5-bis (1,3,6,8-tetra-butyl -N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:4305。 Mass molecular ion peak: 4305. 元素分析按化学式C300H406N12O8计算:C:83.6%;H:9.5%;N:3.9%;O:3.0%实验值:C:83.3%;H:9.4%;N:3.8%;O:3.2%。 Elemental analysis is calculated according to the formula C300H406N12O8: C: 83.6%; H: 9.5%; N: 3.9%; O: 3.0% Found: C: 83.3%; H: 9.4%; N: 3.8%; O: 3.2%.

实例35:化合物1-3-01的合成化合物1-3-01的合成与实例20一样。 Example 35: Synthesis of Compound 1-3-01 1-3-01 synthesis of Example 20 the same. 只是用的是2.4.6-三甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2.4.6- three-methoxybenzaldehyde instead of 3,5-dimethoxybenzaldehyde. 产物四-[2.4.6-三(N-咔唑)丁氧基]苯基卟啉。 The product of four - [2.4.6- three (N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:3460。 Mass molecular ion peak: 3460. 元素分析按化学式C236H210N16O12计算:C:81.9%;H:6.1%;N:6.5%;O:5.6%实验值:C:82.3%;H:6.0%;N:6.3%;O:5.8%。 Elemental analysis is calculated according to the formula C236H210N16O12: C: 81.9%; H: 6.1%; N: 6.5%; O: 5.6% Found: C: 82.3%; H: 6.0%; N: 6.3%; O: 5.8%.

四-[2.4.6-三(N-咔唑)丁氧基]苯基卟啉 四-[2.4.6-三(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉1-3-01 1-3-02实例36:化合物1-3-02的合成化合物1-3-02的合成与实例20一样。 Four - [2.4.6- three (N- carbazole) butoxy] phenyl porphyrin four - [2.4.6- tri (1,3,6,8-tetra-tert-butyl -N- carbazolyl) butoxy] porphyrin 1-3-011-3-02 Example 36: Synthesis of compounds synthesized 1-3-02 and 1-3-02 in 20 instances of the same. 只是用的是1,3,6,8-四叔丁基咔唑代替咔唑,2.4.6-三甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that in place of 1,3,6,8-tetra-t-butyl-carbazole carbazole, 2.4.6- three-methoxybenzaldehyde instead of 3,5-dimethoxybenzaldehyde. 产物四-[2.4.6-三(1,3,6,8-四叔丁基N-咔唑基)丁氧基]苯基卟啉。 The product four - [2.4.6- tri (1,3,6,8-tetra-tert-butyl-N- carbazolyl) butoxy] phenyl porphyrin. 质谱分子离子峰:6151。 Mass molecular ion peak: 6151. 元素分析按化学式C428H594N16O12计算:C:83.5%;H:9.7%;N:3.6%;O:3.1%实验值:C:83.3%;H:9.4%;N:3.8%;O:3.2%。 Elemental analysis is calculated according to the formula C428H594N16O12: C: 83.5%; H: 9.7%; N: 3.6%; O: 3.1% Found: C: 83.3%; H: 9.4%; N: 3.8%; O: 3.2%.

实例37:化合物2-1-01的合成用150毫升N,N-二甲基甲酰胺作溶剂,加入化合物氢化钠3.0克,咔唑10克和1,4-二溴丁烷20.0克,回流反应6小时。 Example 37: Synthesis of Compound 2-1-01 with 150 ml N, N- dimethylformamide as solvent, was added 3.0 g of sodium hydride compounds, carbazole and 10 g of 1,4-dibromo-butane 20.0 g, reflux The reaction for 6 hours. 冷却,加入50毫升甲醇充分搅拌后过滤,收集的滤液浓缩蒸干,粗产物用环己烷为洗脱剂三氧化二铝为固定相柱层析,即得产物N-(4-溴丁基)咔唑8.2克。 After cooling, 50 ml of methanol was stirred sufficiently collected by filtration and filtrate was concentrated to dryness, the crude product was cyclohexane as eluant to aluminum oxide as the stationary phase column chromatography to give the product N- (4- bromobutyl ) carbazole 8.2 g. 产率45.4%。 Yield of 45.4%.

将化合物3-甲氧基-4-羟基苯甲醛10.0克,吡咯4.4克和N,N-二甲基甲酰胺600毫升加热回流2小时,冷却静止,加入200毫升蒸馏水,过滤,将粗产物用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析,即得产物四-(3-甲氧基-4-羟基)苯基卟啉3.5克。 The compound 3-methoxy-4-hydroxybenzaldehyde 10.0 g, pyrrole 4.4 g and N, N- dimethylformamide 600 ml was heated at reflux for 2 hours, cooled stationary, was added 200 ml of distilled water, filtered and the crude product was dichloromethane as eluant alumina as the stationary phase column chromatography to obtain the product four - (3-methoxy-4-hydroxy) phenyl porphyrin 3.5 g. 产率26.7%。 Yield of 26.7%.

将化合物四-(3-甲氧基4-羟基)苯基卟啉1.0克加入N-(4-溴丁基)咔唑3.0克,三乙胺2.0毫升,N,N-二甲基甲酰胺600毫升,加热搅拌反应12小时。 Compound four - (3-methoxy-4-hydroxy) phenyl porphyrin 1.0 g was added N- (4- bromobutyl) carbazole 3.0 g, 2.0 ml of triethylamine, N, N- dimethylformamide 600 ml, was heated with stirring for 12 hours. 产物用蒸馏水和二氯甲烷萃取,二氯甲烷萃取液浓缩,用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析即得产物四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉(H2TCBOPP)1.9克。 The product was extracted with distilled water and methylene chloride, methylene chloride extract was concentrated, diluted with methylene chloride as eluant alumina as the stationary phase column chromatography to obtain the product of four - [3-methoxy -4- (N - carbazole) butoxy] porphyrin (H2TCBOPP) 1.9 grams. 产率:90.1%。 Yield: 90.1%.

将化合物四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉1.0克加入醋酸锌1.0克,丙酸600毫升,加热搅拌反应12小时。 Compound IV - [3-methoxy -4- (N- carbazole) butoxy] phenyl porphyrin was added 1.0 g of zinc acetate, 1.0 g, propionic acid 600 ml, was heated with stirring for 12 hours. 产物用蒸馏水和二氯甲烷萃取,二氯甲烷萃取液浓缩,用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析即得产物四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉锌0.9克。 The product was extracted with distilled water and methylene chloride, methylene chloride extract was concentrated, diluted with methylene chloride as eluant alumina as the stationary phase column chromatography to obtain the product of four - [3-methoxy -4- (N - carbazole) butoxy] 0.9 grams of zinc porphyrin. 产率:86.9%。 Yield: 86.9%. 质谱分子离子峰:1745。 Mass molecular ion peak: 1745. 元素分析按化学式C112H96N8O8Zn计算:C:77.0%; Elemental analysis is calculated according to the formula C112H96N8O8Zn: C: 77.0%; 四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉锌2-1-01H:5.5%;N:6.4%;O:7.3%实验值:C:76.8%;H:5.8%;N:6.7%;O:7.4%。 Four - [3-methoxy -4- (N- carbazolyl) butoxy] phenyl porphyrin zinc 2-1-01H: 5.5%; N: 6.4%; O: 7.3% Found: C: 76.8 %; H: 5.8%; N: 6.7%; O: 7.4%.

实例38:化合物2-1-02的合成化合物2-1-02的合成与实例37一样。 Example 38: Synthesis of Compound Compound Synthesis Example 2-1-02 2-1-02 37 of the same. 只是用的是1,5-二溴戊烷代替1,4-二溴丁烷。 Except that 1,5-dibromopentane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)戊氧基]苯基卟啉锌。 The product four - [3-methoxy -4- (N- carbazole) pentyloxy] phenyl porphyrin zinc. 质谱分子离子峰:1801。 Mass molecular ion peak: 1801. 元素分析按化学式C116H104N8O8Zn计算:C:77.3%;H:5.8%;N:6.2%;O:7.1%;实验值:C:77.8%;H:6.0%;N:6.5%;O:7.0%。 Elemental analysis by chemical formula C116H104N8O8Zn calculation: C: 77.3%; H: 5.8%; N: 6.2%; O: 7.1%; Found: C: 77.8%; H: 6.0%; N: 6.5%; O: 7.0%.

实例39:化合物2-1-03的合成化合物2-1-03的合成与实例37一样。 Example 39: Synthesis of Compound Synthesis Example 2-1-03 2-1-03 37 of the same. 只是用的是1,6-二溴己烷代替1,4-二溴丁烷。 Except that 1,6-dibromohexane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)己氧基]苯基卟啉锌。 The product four - [3-methoxy -4- (N- carbazole) hexyloxy] phenyl porphyrin zinc. 质谱分子离子峰:1857。 Mass molecular ion peak: 1857. 元素分析按化学式C120H112N8O8Zn计算:C:77.5%;H:6.1%;N:6.0%;O:6.9%;实验值:C:77.2%;H:6.3%;N:6.1%;O:7.0%。 Elemental analysis by chemical formula C120H112N8O8Zn calculation: C: 77.5%; H: 6.1%; N: 6.0%; O: 6.9%; Found: C: 77.2%; H: 6.3%; N: 6.1%; O: 7.0%.

实例40:化合物2-1-04的合成化合物2-1-04的合成与实例37一样。 Example 40: Synthesis of Compound Synthesis Example 2-1-04 2-1-04 37 of the same. 只是用的是1,7-二溴庚烷代替1,4-二溴丁烷。 Except that 1,7-dibromoheptane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)庚氧基]苯基卟啉锌。 The product four - [3-methoxy -4- (N- carbazole) heptyloxy] phenyl porphyrin zinc. 质谱分子离子峰:1913。 Mass molecular ion peak: 1913. 元素分析按化学式C124H120N8O8Zn计算:C:77.7%;H:6.3%;N:5.9%;O:6.7%;实验值:C:77.9%;H:6.2%;N:6.1%;O:7.0%。 Elemental analysis by chemical formula C124H120N8O8Zn calculation: C: 77.7%; H: 6.3%; N: 5.9%; O: 6.7%; Found: C: 77.9%; H: 6.2%; N: 6.1%; O: 7.0%.

实例41:化合物2-1-05的合成化合物2-1-05的合成与实例37一样。 Example 41: Synthesis of Compound Synthesis Example 2-1-05 2-1-05 37 of the same. 只是用的是1,8-二溴辛烷代替1,4-二溴丁烷。 Except that 1,8-dibromo-octane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)辛氧基]苯基卟啉锌。 The product four - [3-methoxy -4- (N- carbazole) octyloxy] phenyl porphyrin zinc. 质谱分子离子峰:1969。 Mass molecular ion peak: 1969. 元素分析按化学式C128H128N8O8Zn计算:C:78.0%;H:6.5%;N:5.7%;O:6.5%;实验值:C:77.9%;H:6.2%;N:6.0%;O:6.4%。 Elemental analysis by chemical formula C128H128N8O8Zn calculation: C: 78.0%; H: 6.5%; N: 5.7%; O: 6.5%; Found: C: 77.9%; H: 6.2%; N: 6.0%; O: 6.4%.

实例42:化合物2-1-06的合成化合物2-1-06的合成与实例37一样。 Example 42: Synthesis of Compound Synthesis Example 2-1-06 2-1-06 37 of the same. 只是用的是1,9-二溴壬烷代替1,4-二溴丁烷。 Except that 1,9-dibromo-nonane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)壬氧基]苯基卟啉锌。 The product four - [3-methoxy -4- (N- carbazole) nonyl oxy] phenyl porphyrin zinc. 质谱分子离子峰:2025。 Mass molecular ion peak: 2025. 元素分析按化学式C132H136N8O8Zn计算:C:78.2%;H:6.8%;N:5.5%;O:6.3%;实验值:C:77.8%;H:6.9%;N:5.4%;O:6.4%。 Elemental analysis by chemical formula C132H136N8O8Zn calculation: C: 78.2%; H: 6.8%; N: 5.5%; O: 6.3%; Found: C: 77.8%; H: 6.9%; N: 5.4%; O: 6.4%.

实例43:化合物2-1-07的合成化合物2-1-07的合成与实例37一样。 Example 43: Synthesis of Compound Synthesis Example 2-1-07 2-1-07 37 of the same. 只是用的是1,10-二溴癸烷代替1,4-二溴丁烷。 Except that the 1,10-dibromodecane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)癸氧基]苯基卟啉锌。 The product four - [3-methoxy -4- (N- carbazole) decyloxy] phenyl porphyrin zinc. 质谱分子离子峰:2081。 Mass molecular ion peak: 2081. 元素分析按化学式C136H144N8O8Zn计算:C:78.4%;H:7.0%;N:5.4%;O:6.1%;实验值:C:78.5%;H:7.2%;N:5.5%;O:6.2%。 Elemental analysis by chemical formula C136H144N8O8Zn calculation: C: 78.4%; H: 7.0%; N: 5.4%; O: 6.1%; Found: C: 78.5%; H: 7.2%; N: 5.5%; O: 6.2%.

实例44:化合物2-1-08的合成化合物2-1-08的合成与实例37一样。 Example 44: Synthesis of Compound 2-1-08 2-1-08 synthesis of Example 37 the same. 只是用的是1,11-二溴十一烷代替1,4-二溴丁烷。 Except that 1,11-dibromo-undecane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)十一烷氧基]苯基卟啉锌。 The product four - [3-methoxy -4- (N- carbazole) undecanoic oxy] phenyl porphyrin zinc. 质谱分子离子峰:2137。 Mass molecular ion peak: 2137. 元素分析按化学式C140H152N8O8Zn计算:C:78.6%;H:7.2%;N:5.2%;O:6.0%;实验值:C:79.1%;H:7.3%;N:5.1%;O:6.2%。 Elemental analysis by chemical formula C140H152N8O8Zn calculation: C: 78.6%; H: 7.2%; N: 5.2%; O: 6.0%; Found: C: 79.1%; H: 7.3%; N: 5.1%; O: 6.2%.

实例45:化合物2-1-09的合成化合物2-1-09的合成与实例37一样。 Example 45: Synthesis of Compound Synthesis Example 2-1-09 2-1-09 37 of the same. 只是用的是1,12-二溴十二烷代替1,4-二溴丁烷。 Except that the 1,12-dibromo dodecane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)十二烷氧基]苯基卟啉锌。 The product four - [3-methoxy -4- (N- carbazole) dodecyloxy] phenyl porphyrin zinc. 质谱分子离子峰:2193。 Mass molecular ion peak: 2193. 元素分析按化学式C144H160N8O8Zn计算:C:78.8%;H:7.3%;N:5.1%;O:5.8%;实验值:C:79.2%;H:7.1%;N:5.2%;O:6.0%。 Elemental analysis by chemical formula C144H160N8O8Zn calculation: C: 78.8%; H: 7.3%; N: 5.1%; O: 5.8%; Found: C: 79.2%; H: 7.1%; N: 5.2%; O: 6.0%.

实例46:化合物2-1-10的合成化合物2-1-10的合成与实例37一样。 Example 46: Synthesis of Compound Synthesis Example 2-1-10 2-1-10 37 of the same. 只是用的是3-乙氧基4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-ethoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-乙氧基-4-(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [3-ethoxy -4- (N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:1801。 Mass molecular ion peak: 1801. 元素分析按化学式C116H104N8O8Zn计算:C:77.3%;H:5.8%;N:6.2%;O:7.1%;实验值:C:77.1%;H:6.0%;N:6.5%;O:7.3%。 Elemental analysis by chemical formula C116H104N8O8Zn calculation: C: 77.3%; H: 5.8%; N: 6.2%; O: 7.1%; Found: C: 77.1%; H: 6.0%; N: 6.5%; O: 7.3%.

四-[3-乙氧基-4-(N-咔唑)丁氧基]苯基卟啉锌 四-[3-丙氧基-4-(N-咔唑)丁氧基]苯基卟啉锌2-1-10 2-1-11实例47:化合物2-1-11的合成化合物2-1-11的合成与实例37一样。 Four - [3-ethoxy -4- (N- carbazole) butoxy] phenyl porphyrin zinc four - [3-propoxy -4- (N- carbazole) butoxy] phenyl porphyrin morpholino zinc 2-1-102-1-11 Example 47: Synthesis of compound 2-1-11 2-1-11 Example 37 Synthesis and the same. 只是用的是3-丙氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-propoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-丙氧基-4-(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [3-propoxy -4- (N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:1857。 Mass molecular ion peak: 1857. 元素分析按化学式C120H112N8O8Zn计算:C:77.5%;H:6.1%;N:6.0%;O:6.9%;实验值:C:77.7%;H:6.3%;N:6.1%;O:7.1%。 Elemental analysis by chemical formula C120H112N8O8Zn calculation: C: 77.5%; H: 6.1%; N: 6.0%; O: 6.9%; Found: C: 77.7%; H: 6.3%; N: 6.1%; O: 7.1%.

实例48:化合物2-1-12的合成化合物2-1-12的合成与实例37一样。 Example 48: Synthesis of Compound Synthesis Example 2-1-12 2-1-12 37 of the same. 只是用的是3-丁氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-butoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-丁氧基-4-(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [3-butoxy--4- (N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:1913。 Mass molecular ion peak: 1913. 元素分析按化学式C124H120N8O8Zn计算:C:77.7%;H:6.3%;N:5.9%;O:6.7%;实验值:C:77.2%;H:6.2%;N:6.1%;O:6.6%。 Elemental analysis by chemical formula C124H120N8O8Zn calculation: C: 77.7%; H: 6.3%; N: 5.9%; O: 6.7%; Found: C: 77.2%; H: 6.2%; N: 6.1%; O: 6.6%.

实例49:化合物2-1-13的合成化合物2-1-13的合成与实例37一样。 Example 49: Synthesis of Compound Synthesis Example 2-1-13 2-1-13 37 of the same. 只是用的是3-叔丁氧基4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-tert-butoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-叔丁氧基-4-(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [3-tert-butoxy -4- (N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:1913。 Mass molecular ion peak: 1913. 元素分析按化学式C124H120N8O8Zn计算:C:77.7%;H:6.3%;N:5.9%;O:6.7%;实验值:C:77.8%; Elemental analysis is calculated according to the formula C124H120N8O8Zn: C: 77.7%; H: 6.3%; N: 5.9%; O: 6.7%; Found: C: 77.8%; 四-[3-丁氧基-4-(N-咔唑)丁氧基]苯基卟啉锌 四-[3-叔丁氧基-4-(N-咔唑)丁氧基]苯基卟啉锌2-1-12 2-1-13H:6.2%;N:6.1%;O:6.9%。 Four - [3-butoxy -4- (N- carbazolyl) butoxy] zinc porphyrin four - [3-tert-butoxide -4- (N- carbazolyl) butoxy] phenyl zinc porphyrin 2-1-12 2-1-13H: 6.2%; N: 6.1%; O: 6.9%.

实例50:化合物2-1-14的合成化合物2-1-14的合成与实例37一样。 Example 50: Synthesis of Compound Compound Synthesis Example 2-1-14 2-1-14 37 of the same. 只是用的是4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[4-(N-咔唑)丁氧基]苯基卟啉锌。 The product of four - [4- (N- carbazolyl) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:1625。 Mass molecular ion peak: 1625. 元素分析按化学式C108H88N8O8Zn计算:C:79.7%;H:5.5%;N:6.9%;O:3.9%;实验值:C:79.3%;H:5.4%;N:7.0%;O:4.1%。 Elemental analysis by chemical formula C108H88N8O8Zn calculation: C: 79.7%; H: 5.5%; N: 6.9%; O: 3.9%; Found: C: 79.3%; H: 5.4%; N: 7.0%; O: 4.1%.

实例51:化合物2-1-15的合成化合物2-1-15的合成与实例37一样。 Example 51: Synthesis of Compound Compound Synthesis Example 2-1-15 2-1-15 37 of the same. 只是用的是3-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-(N-咔唑)丁氧基]苯基卟啉锌。 The product of four - [3- (N- carbazolyl) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:1625。 Mass molecular ion peak: 1625. 元素分析按化学式C108H88N8O8Zn计算:C:79.7%;H:5.5%;N:6.9%;O:3.9%;实验值:C:79.9%;H:5.4%;N:7.0%;O:3.7%。 Elemental analysis by chemical formula C108H88N8O8Zn calculation: C: 79.7%; H: 5.5%; N: 6.9%; O: 3.9%; Found: C: 79.9%; H: 5.4%; N: 7.0%; O: 3.7%.

四-[4-(N-咔唑)丁氧基]苯基卟啉锌 四-[3-(N-咔唑)丁氧基]苯基卟啉锌2-1-14 2-1-15实例52:化合物2-1-16的合成化合物2-1-16的合成与实例37一样。 Four - [4- (N- carbazolyl) butoxy] zinc porphyrin four - [3- (N- carbazolyl) butoxy] porphyrin zinc 2-1-142-1-15 Example 52: Synthesis of Compound Compound Synthesis Example 2-1-16 2-1-16 37 of the same. 只是用的是3.5-二甲氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3.5-dimethoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[2.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [2.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:1865。 Mass molecular ion peak: 1865. 元素分析按化学式C116H104N8O12Zn计算:C:74.6%;H:5.6%;N:6.0%;O:10.3%;实验值:C:74.3%;H:5.8%;N:6.1%:O:10.1%。 Elemental analysis by chemical formula C116H104N8O12Zn calculation: C: 74.6%; H: 5.6%; N: 6.0%; O: 10.3%; Found: C: 74.3%; H: 5.8%; N: 6.1%: O: 10.1%.

实例53:化合物2-1-17的合成化合物2-1-17的合成与实例37一样。 Example 53: Synthesis of Compound Compound Synthesis Example 2-1-17 2-1-17 37 of the same. 只是用的是2.5-二甲氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 2.5-dimethoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[2.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [2.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:1803。 Mass molecular ion peak: 1803. 元素分析按化学式C116H104N8O12Zn计算:C:74.6%;H:5.6%;N:6.0%;O:10.3%;实 Elemental analysis is calculated according to the formula C116H104N8O12Zn: C: 74.6%; H: 5.6%; N: 6.0%; O: 10.3%; real 四-[3.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉锌 四-[2.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉锌2-1-16 2-1-17验值:C:74.8%;H:5.8%;N:6.1%;O:10.4%。 Four - [3.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin zinc four - [2.5-dimethoxy -4- (N- carbazole) butoxy] benzene porphyrin zinc 2-1-162-1-17 check value: C: 74.8%; H: 5.8%; N: 6.1%; O: 10.4%.

实例54:化合物2-1-18的合成化合物2-1-18的合成与实例37一样。 Example 54: Synthesis of Compound 2-1-18 2-1-18 synthesis of Example 37 the same. 只是用的是3,6-二叔丁基咔唑代替咔唑。 Except that instead of 3,6-di-t-butyl-carbazole carbazole. 产物四-[3-甲氧基-4-(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉锌。 The product four - [3-methoxy-4- (3,6-di-tert -N- carbazolyl) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:2193。 Mass molecular ion peak: 2193. 元素分析按化学式C144H160N8O8Zn计算:C:78.8%;H:7.3%;N:5.1%;O:5.8%;实验值:C:78.4%;H:7.5%;N:5.0%;O:5.9%。 Elemental analysis by chemical formula C144H160N8O8Zn calculation: C: 78.8%; H: 7.3%; N: 5.1%; O: 5.8%; Found: C: 78.4%; H: 7.5%; N: 5.0%; O: 5.9%.

实例55:化合物2-1-19的合成化合物2-1-19的合成与实例37一样。 Example 55: Synthesis of Compound Compound Synthesis Example 2-1-19 2-1-19 37 of the same. 只是用的是1,3,6,8-四叔丁基咔唑代替咔唑。 Except that in place of 1,3,6,8-tetra-tert-butyl-carbazole carbazole. 产物四-[3-甲氧基-4-(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉锌。 The product four - [3-methoxy-4- (1,3,6,8-tetra-tert-butyl -N- carbazolyl) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:2642。 Mass molecular ion peak: 2642. 元素分析按化学式C176H224N8O8Zn计算:C:79.9%;H:8.5%;N:4.2%;O:4.8%;实验值:C:80.4%;H:8.3%;N:4.1%;O:5.0%。 Elemental analysis by chemical formula C176H224N8O8Zn calculation: C: 79.9%; H: 8.5%; N: 4.2%; O: 4.8%; Found: C: 80.4%; H: 8.3%; N: 4.1%; O: 5.0%.

四-[3-甲氧基-4-(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉锌 四-[3-甲氧基-4-(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉锌2-1-18 2-1-19实例56:化合物2-2-01的合成用150毫升N,N-二甲基甲酰胺作溶剂,加入化合物氢化钠3.0克,咔唑10克和1,4-二溴丁烷20.0克,回流反应6小时。 Four - [3-methoxy-4- (3,6-di-t-butyl -N- carbazol-yl) butoxy] phenyl porphyrin zinc four - [3-methoxy-4- (1, 3,6,8-tetra-t-butyl -N- carbazolyl) butoxy] phenyl porphyrin zinc 2-1-182-1-19 Example 56: Synthesis of Compound 2-2-01 with 150 ml N, N- dimethylformamide as solvent, was added 3.0 g of sodium hydride compounds, carbazole and 10 g of 1,4-dibromo-butane 20.0 g, the reaction was refluxed for 6 hours. 冷却,加入50毫升甲醇充分搅拌后过滤,收集的滤液浓缩蒸干,粗产物用环己烷为洗脱剂三氧化二铝为固定相柱层析,即得产物N-(4-溴丁基)咔唑8.2克。 After cooling, 50 ml of methanol was stirred sufficiently collected by filtration and filtrate was concentrated to dryness, the crude product was cyclohexane as eluant to aluminum oxide as the stationary phase column chromatography to give the product N- (4- bromobutyl ) carbazole 8.2 g. 产率45.4%。 Yield of 45.4%.

将化合物3.5-二甲氧基苯甲醛10.0克,吡咯4.0克和N,N-二甲基甲酰胺600毫升加热回流2小时,冷却静止,加入200毫升蒸馏水,过滤,将粗产物用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析,即得产物四-(3.5-二甲氧基)苯基卟啉2.8克。 The compound 3,5-methoxybenzaldehyde 10.0 g, pyrrole 4.0 g and N, N- dimethylformamide 600 ml was heated at reflux for 2 hours, cooled stationary, was added 200 ml of distilled water, filtered and the crude product with dichloromethane as eluant to aluminum oxide as the stationary phase column chromatography to obtain the product of four - (3,5-dimethoxyphenyl) porphyrin 2.8 g. 产率21.8%。 Yield of 21.8%.

将化合物四-(3.5-二甲氧基)苯基卟啉2.0克加入三溴化硼1毫升,甲醇100毫升,加热回流反应3小时,冷却静止,加入100毫升0.1M稀盐酸,减压蒸馏蒸干溶剂,二氯甲烷洗涤,即得产物四-(3.5-二羟基)苯基卟啉1.7克。 Compound four - (3,5-dimethoxyphenyl) porphyrin 2.0 g of boron tribromide was added 1 ml, 100 ml of methanol was heated under reflux for 3 hours, cooled stationary, dilute hydrochloric acid was added 100 ml 0.1M, vacuum distillation The solvent was evaporated, washed with methylene chloride, that was the product of four - (3,5-hydroxy) phenyl porphyrin 1.7 g. 产率98%。 98% yield.

将化合物四-(3.5-二羟基)苯基卟啉1.0克加入N-(4-溴丁基)咔唑6.0克,三乙胺2.0毫升,N,N-二甲基甲酰胺600毫升,加热搅拌反应12小时。 Compound four - (3,5-dihydroxy) phenyl porphyrin 1.0 g was added N- (4- bromobutyl) carbazole 6.0 g, 2.0 ml of triethylamine, N, N- dimethylformamide, 600 ml, was heated The reaction was stirred for 12 hours. 产物用蒸馏水和二氯甲烷萃取,二氯甲烷萃取液浓缩,用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析即得产物四-[3.5-二(N-咔唑)丁氧基]苯基卟啉2.9克。 The product was extracted with distilled water and methylene chloride, methylene chloride extract was concentrated, diluted with methylene chloride as eluant alumina as the stationary phase column chromatography to obtain the product of four - [3,5-(N- carbazole) butanoate oxy] phenyl porphyrin 2.9 g. 产率:85.6%。 Yield: 85.6%.

将化合物四-[3.5-二(N-咔唑)丁氧基]苯基卟啉1.0克加入醋酸锌1.0克,丙酸600毫升,加热搅拌反应12小时。 Compound IV - [3,5-(N- carbazole) butoxy] phenyl porphyrin was added 1.0 g of zinc acetate, 1.0 g, propionic acid 600 ml, was heated with stirring for 12 hours. 产物用蒸馏水和二氯甲烷萃取,二氯甲烷萃取液浓缩,用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析即得产物四-[3.5-二(N-咔唑)丁氧基]苯基卟啉锌0.8克。 The product was extracted with distilled water and methylene chloride, methylene chloride extract was concentrated, diluted with methylene chloride as eluant alumina as the stationary phase column chromatography to obtain the product of four - [3,5-(N- carbazole) butanoate oxy] phenyl porphyrin zinc 0.8 g. 产率:78.1%。 Yield: 78.1%. 质谱分子离子峰:2573。 Mass molecular ion peak: 2573. 元素分析按化学式C172H148N12O8Zn计算:C:80.2%;H:5.8%;N:6.5%;O:5.0%实验值:C:79.9%;H:5.6%;N:6.4%;O:5.1%。 Elemental analysis is calculated according to the formula C172H148N12O8Zn: C: 80.2%; H: 5.8%; N: 6.5%; O: 5.0% Found: C: 79.9%; H: 5.6%; N: 6.4%; O: 5.1%.

四-[3.5-二(N-咔唑)丁氧基]苯基卟啉锌2-2-01实例57:化合物2-2-02的合成化合物2-2-02的合成与实例56一样。 Four - [3,5-(N- carbazole) butoxy] phenyl porphyrin zinc 2-2-01 Example 57: Synthesis of Compound Compound Synthesis Example 2-2-02 2-2-02 56 of the same. 只是用的是1,5-二溴戊烷代替1,4-二溴丁烷。 Except that 1,5-dibromopentane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)戊氧基]苯基卟啉锌。 The product four - [3,5-(N- carbazole) pentyloxy] phenyl porphyrin zinc. 质谱分子离子峰:2685。 Mass molecular ion peak: 2685. 元素分析按化学式C180H164N12O8Zn计算:C:80.4%;H:6.2%;N:6.3%;O:4.8%;实验值:C:80.8%;H:6.1%;N:6.5%;O:4.7%。 Elemental analysis by chemical formula C180H164N12O8Zn calculation: C: 80.4%; H: 6.2%; N: 6.3%; O: 4.8%; Found: C: 80.8%; H: 6.1%; N: 6.5%; O: 4.7%.

实例58:化合物2-2-03的合成化合物2-2-03的合成与实例56一样。 Example 58: Synthesis of Compound Synthesis Example 2-2-03 2-2-03 56 of the same. 只是用的是1,6-二溴己烷代替1,4-二溴丁烷。 Except that 1,6-dibromohexane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)己氧基]苯基卟啉锌。 The product four - [3,5-(N- carbazole) hexyloxy] phenyl porphyrin zinc. 质谱分子离子峰:2797。 Mass molecular ion peak: 2797. 元素分析按化学式C188H180N12O8Zn计算:C:80.6%;H:6.5%;N:6.0%;O:4.3%;实验值:C:80.2%;H:6.2%;N:6.1%;O:4.2%。 Elemental analysis by chemical formula C188H180N12O8Zn calculation: C: 80.6%; H: 6.5%; N: 6.0%; O: 4.3%; Found: C: 80.2%; H: 6.2%; N: 6.1%; O: 4.2%.

实例59:化合物2-2-04的合成化合物2-2-04的合成与实例56一样。 Example 59: Synthesis of Compound Synthesis Example 2-2-04 2-2-04 56 of the same. 只是用的是1,7-二溴庚烷代替1,4-二溴丁烷。 Except that 1,7-dibromoheptane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)庚氧基]苯基卟啉锌。 The product four - [3,5-(N- carbazole) heptyloxy] phenyl porphyrin zinc. 质谱分子离子峰:2909。 Mass molecular ion peak: 2909. 元素分析按化学式C196H196N12O8Zn计算:C:80.8%;H:6.8%;N:5.8%;O:4.4%;实验值:C:81.2%;H:6.9%;N:6.0%;O:4.2%。 Elemental analysis by chemical formula C196H196N12O8Zn calculation: C: 80.8%; H: 6.8%; N: 5.8%; O: 4.4%; Found: C: 81.2%; H: 6.9%; N: 6.0%; O: 4.2%.

实例60:化合物2-2-05的合成化合物2-2-05的合成与实例56一样。 Example 60: Synthesis of Compound Synthesis Example 2-2-05 2-2-05 56 of the same. 只是用的是1,8-二溴辛烷代替1,4-二溴丁烷。 Except that 1,8-dibromo-octane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)辛氧基]苯基卟啉锌。 The product four - [3,5-(N- carbazole) octyloxy] phenyl porphyrin zinc. 质谱分子离子峰:3022。 Mass molecular ion peak: 3022. 元素分析按化学式C204H212N12O8Zn计算:C:81.0%;H:7.1%;N:5.6%;O:4.2%;实验值:C:80.9%;H:7.2%;N:5.3%;O:4.4%。 Elemental analysis by chemical formula C204H212N12O8Zn calculation: C: 81.0%; H: 7.1%; N: 5.6%; O: 4.2%; Found: C: 80.9%; H: 7.2%; N: 5.3%; O: 4.4%.

实例61:化合物2-2-06的合成化合物2-2-06的合成与实例56一样。 Example 61: Synthesis of Compound Synthesis Example 2-2-06 2-2-06 56 of the same. 只是用的是1,9-二溴壬烷代替1,4-二溴丁烷。 Except that 1,9-dibromo-nonane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)壬氧基]苯基卟啉锌。 The product four - [3,5-(N- carbazole) nonyl oxy] phenyl porphyrin zinc. 质谱分子离子峰:3134。 Mass molecular ion peak: 3134. 元素分析按化学式C212H228N12O8Zn计算:C:81.2%;H:7.3%;N:5.4%;O:4.1%;实验值:C:81.1%;H:7.4%;N:5.5%;O:4.0%。 Elemental analysis by chemical formula C212H228N12O8Zn calculation: C: 81.2%; H: 7.3%; N: 5.4%; O: 4.1%; Found: C: 81.1%; H: 7.4%; N: 5.5%; O: 4.0%.

实例62:化合物2-2-07的合成化合物2-2-07的合成与实例56一样。 Example 62: Synthesis of Compound Synthesis Example 2-2-07 2-2-07 56 of the same. 只是用的是1,10-二溴癸烷代替1,4-二溴丁烷。 Except that the 1,10-dibromodecane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)癸氧基]苯基卟啉锌。 The product four - [3,5-(N- carbazole) decyloxy] phenyl porphyrin zinc. 质谱分子离子峰:3246。 Mass molecular ion peak: 3246. 元素分析按化学式C220H244N12O8Zn计算:C:81.3%;H:7.6%;N:5.2%;O:3.9%;实验值:C:81.5%;H:7.9%;N:5.0%;O:4.0%。 Elemental analysis by chemical formula C220H244N12O8Zn calculation: C: 81.3%; H: 7.6%; N: 5.2%; O: 3.9%; Found: C: 81.5%; H: 7.9%; N: 5.0%; O: 4.0%.

实例63:化合物2-2-08的合成化合物2-2-08的合成与实例56一样。 Example 63: Synthesis of Compound 2-2-08 2-2-08 synthesis of Example 56 the same. 只是用的是1,11-二溴十一烷代替1,4-二溴丁烷。 Except that 1,11-dibromo-undecane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)十一烷氧基]苯基卟啉锌。 The product four - [3,5-(N- carbazole) undecanoic oxy] phenyl porphyrin zinc. 质谱分子离子峰:3358。 Mass molecular ion peak: 3358. 元素分析按化学式C228H260N12O8Zn计算:C:81.5%;H:7.8%;N:5.0%;O:3.8%;实验值:C:81.2%;H:8.0%;N:5.2%;O:3.7%。 Elemental analysis by chemical formula C228H260N12O8Zn calculation: C: 81.5%; H: 7.8%; N: 5.0%; O: 3.8%; Found: C: 81.2%; H: 8.0%; N: 5.2%; O: 3.7%.

实例64:化合物2-2-09的合成化合物2-2-09的合成与实例56一样。 Example 64: Synthesis of Compound Synthesis Example 2-2-09 2-2-09 56 of the same. 只是用的是1,12-二溴十二烷代替1,4-二溴丁烷。 Except that the 1,12-dibromo dodecane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)十二烷氧基]苯基卟啉锌。 The product four - [3,5-(N- carbazole) dodecyloxy] phenyl porphyrin zinc. 质谱分子离子峰:3470。 Mass molecular ion peak: 3470. 元素分析按化学式C236H276N12O8Zn计算:C:81.6%;H:8.0%;N:4.8%;O:3.7%;实验值:C:81.2%;H:8.3%;N:5.0%;O:3.8%。 Elemental analysis by chemical formula C236H276N12O8Zn calculation: C: 81.6%; H: 8.0%; N: 4.8%; O: 3.7%; Found: C: 81.2%; H: 8.3%; N: 5.0%; O: 3.8%.

实例65:化合物2-2-10的合成化合物2-2-10的合成与实例56一样。 Example 65: Synthesis of Compound Synthesis Example 2-2-10 2-2-10 56 same. 只是用的是3.4-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 3,4-dimethoxybenzaldehyde in place of 3,5-dimethoxybenzaldehyde. 产物四-[3.4-二(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [3.4 two (N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:2573。 Mass molecular ion peak: 2573. 元素分析按化学式C172H148N12O8Zn计算:C:80.2%;H:5.8%;N:6.5%;O:5.0%实验值:C:79.9%;H:5.7%;N:6.4%;O:5.2%。 Elemental analysis is calculated according to the formula C172H148N12O8Zn: C: 80.2%; H: 5.8%; N: 6.5%; O: 5.0% Found: C: 79.9%; H: 5.7%; N: 6.4%; O: 5.2%.

四-[3.4-二(N-咔唑)丁氧基]苯基卟啉锌 四-[2.5-二(N-咔唑)丁氧基]苯基卟啉锌2-2-10 2-2-11 Four - [3.4-two (N- carbazole) butoxy] phenyl porphyrin zinc four - [2,5-di (N- carbazole) butoxy] phenyl porphyrin zinc 2-2-102-2 -11

实例66:化合物2-2-11的合成化合物2-2-11的合成与实例56一样。 Example 66: Synthesis of Compound 2-2-11 2-2-11 synthesis of Example 56 the same. 只是用的是2.5-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2,5-dimethyl-methoxybenzaldehyde instead of 3,5-dimethoxybenzaldehyde. 产物四-[2.5-二(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [2,5-dimethyl (N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:2573。 Mass molecular ion peak: 2573. 元素分析按化学式C172H148N12O8Zn计算:C:80.2%;H:5.8%;N:6.5%;O:5.0%实验值:C:79.9%;H:5.6%;N:6.2%;O:4.9%。 Elemental analysis is calculated according to the formula C172H148N12O8Zn: C: 80.2%; H: 5.8%; N: 6.5%; O: 5.0% Found: C: 79.9%; H: 5.6%; N: 6.2%; O: 4.9%.

实例67:化合物2-2-12的合成化合物2-2-12的合成与实例56一样。 Example 67: Synthesis of Compound Compound Synthesis Example 2-2-12 2-2-12 56 of the same. 只是用的是2.4-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2,4-dimethoxybenzaldehyde in place of 3,5-dimethoxybenzaldehyde. 产物四-[2.4-二(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [2.4-(N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:2573。 Mass molecular ion peak: 2573. 元素分析按化 Elemental analysis by technology 四-[2.4-二(N-咔唑)丁氧基]苯基卟啉锌 四-[2.6-二(N-咔唑)丁氧基]苯基卟啉锌2-2-12 2-2-13学式C172H148N12O8Zn计算:C:80.2%;H:5.8%;N:6.5%;O:5.0%实验值:C:79.7%;H:5.6%;N:6.8%;O:5.1%。 Four - [2.4-(N- carbazole) butoxy] phenyl porphyrin zinc four - [2,6-two (N- carbazole) butoxy] phenyl porphyrin zinc 2-2-122-2 -13 C172H148N12O8Zn chemical formula is calculated: C: 80.2%; H: 5.8%; N: 6.5%; O: 5.0% Found: C: 79.7%; H: 5.6%; N: 6.8%; O: 5.1%.

实例68:化合物2-2-13的合成化合物2-2-13的合成与实例56一样。 Example 68: Synthesis of Synthesis of Compound of Example 56 Compound 2-2-13 2-2-13 the same. 只是用的是2.6-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2,6-dimethoxybenzaldehyde in place of 3,5-dimethoxybenzaldehyde. 产物四-[2.6-二(N-咔唑)丁氧基]苯基卟啉锌。 The product four - [2,6-two (N- carbazole) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:2573。 Mass molecular ion peak: 2573. 元素分析按化学式C172H148N12O8Zn计算:C:80.2%;H:5.8%;N:6.5%;O:5.0%实验值:C:80.5%;H:5.7%;N:6.4%;O:5.1%。 Elemental analysis is calculated according to the formula C172H148N12O8Zn: C: 80.2%; H: 5.8%; N: 6.5%; O: 5.0% Found: C: 80.5%; H: 5.7%; N: 6.4%; O: 5.1%.

实例69:化合物2-2-14的合成化合物2-2-14的合成与实例56一样。 Example 69: Synthesis of Compound Synthesis Example 2-2-14 2-2-14 56 of the same. 只是用的是3,6-二叔丁基咔唑代替咔唑。 Except that instead of 3,6-di-t-butyl-carbazole carbazole. 产物四-[3,5-二(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉锌。 The product four - [3,5-bis (3,6-di-tert--N- carbazolyl) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:3470。 Mass molecular ion peak: 3470. 元素分析按化学式C236H276N12O8Zn计算:C:81.6%;H:8.0%;N:4.8%;O:3.7%实验值:C:82.0%;H:8.1%;N:4.6%;O:3.9%。 Elemental analysis is calculated according to the formula C236H276N12O8Zn: C: 81.6%; H: 8.0%; N: 4.8%; O: 3.7% Found: C: 82.0%; H: 8.1%; N: 4.6%; O: 3.9%.

四-[3.5-二(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉锌 四-[3.5-二(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉锌2-2-14 2-2-15 Four - [3.5-bis (3,6-di-t-butyl -N- carbazol-yl) butoxy] phenyl porphyrin zinc four - [3.5-bis (1,3,6,8-tetra-tert-butyl -N- carbazolyl) butoxy] porphyrin zinc 2-2-142-2-15

实例70:化合物2-2-15的合成化合物2-2-15的合成与实例56一样。 Example 70: Synthesis of Compound Synthesis Example 2-2-15 2-2-15 56 of the same. 只是用的是1,3,6,8-四叔丁基咔唑代替咔唑。 Except that in place of 1,3,6,8-tetra-tert-butyl-carbazole carbazole. 产物四-[3,5-二(1,3,6,8-四叔丁基N-咔唑基)丁氧基]苯基卟啉锌。 The product four - [3,5-bis (1,3,6,8-tetra-butyl N- carbazolyl) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:4367。 Mass molecular ion peak: 4367. 元素分析按化学式C300H404N12O8Zn计算:C:82.4%;H:9.3%;N:3.8%;O:2.9%实验值:C:82.3%;H:9.4%;N:3.7%;O:3.0%。 Elemental analysis is calculated according to the formula C300H404N12O8Zn: C: 82.4%; H: 9.3%; N: 3.8%; O: 2.9% Found: C: 82.3%; H: 9.4%; N: 3.7%; O: 3.0%.

实例71:化合物2-3-01的合成化合物2-3-01的合成与实例56一样。 Example 71: Synthesis of Compound 2-3-01 2-3-01 synthesis of Example 56 the same. 只是用的是2.4.6-三甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2.4.6- three-methoxybenzaldehyde instead of 3,5-dimethoxybenzaldehyde. 产物四-[2.4.6-三(N-咔唑)丁氧基]苯基卟啉锌。 The product of four - [2.4.6- three (N- carbazolyl) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:3522。 Mass molecular ion peak: 3522. 元素分析 Elemental analysis 四-[2.4.6-三(N-咔唑)丁氧基]苯基卟啉锌 四-[2.4.6-三(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉锌2-3-01 2-3-02按化学式C236H208N16O12Zn计算:C:80.4%;H:6.0%;N:6.4%;O:5.5%实验值:C:80.3%;H:6.2%;N:6.3%;O:5.4%。 Four - [2.4.6- three (N- carbazole) butoxy] phenyl porphyrin zinc four - [2.4.6- tri (1,3,6,8-tetra-tert-butyl -N- carbazolyl ) butoxy] porphyrin zinc 2-3-012-3-02 is calculated according to the formula C236H208N16O12Zn: C: 80.4%; H: 6.0%; N: 6.4%; O: 5.5% Found: C: 80.3 %; H: 6.2%; N: 6.3%; O: 5.4%.

实例72:化合物2-3-02的合成化合物2-3-02的合成与实例56一样。 Example 72: Synthesis of Compound Compound Synthesis Example 2-3-02 2-3-02 56 of the same. 只是用的是1,3,6,8-四叔丁基咔唑代替咔唑,2.4.6-三甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that in place of 1,3,6,8-tetra-t-butyl-carbazole carbazole, 2.4.6- three-methoxybenzaldehyde instead of 3,5-dimethoxybenzaldehyde. 产物四-[2.4.6-三(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉锌。 The product four - [2.4.6- tri (1,3,6,8-tetra-tert-butyl -N- carbazol-yl) butoxy] phenyl porphyrin zinc. 质谱分子离子峰:6213。 Mass molecular ion peak: 6213. 元素分析按化学式C428H592N16O12Zn计算:C:82.7%;H:9.6%;N:3.6%;O:3.1%实验值:C:83.0%;H:9.4%;N:3.8%;O:3.2%。 Elemental analysis is calculated according to the formula C428H592N16O12Zn: C: 82.7%; H: 9.6%; N: 3.6%; O: 3.1% Found: C: 83.0%; H: 9.4%; N: 3.8%; O: 3.2%.

实例73:化合物2-1-20的合成 2-1-20 synthetic compounds: Example 73 四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉铂2-1-20用150毫升N,N-二甲基甲酰胺作溶剂,加入化合物氢化钠3.0克,咔唑10克和1,4-二溴丁烷20.0克,回流反应6小时。 Four - [3-methoxy -4- (N- carbazole) butoxy] phenyl porphyrin platinum 2-1-20 with 150 ml of N, N- dimethylformamide as a solvent, the compound was added sodium hydride 3.0 grams, 10 grams carbazole and 1,4-dibromo-butane 20.0 g, the reaction was refluxed for 6 hours. 冷却,加入50毫升甲醇充分搅拌后过滤,收集的滤液浓缩蒸干,粗产物用环己烷为洗脱剂三氧化二铝为固定相柱层析,即得产物N-(4-溴丁基)咔唑8.2克。 After cooling, 50 ml of methanol was stirred sufficiently collected by filtration and filtrate was concentrated to dryness, the crude product was cyclohexane as eluant to aluminum oxide as the stationary phase column chromatography to give the product N- (4- bromobutyl ) carbazole 8.2 g. 产率45.4%。 Yield of 45.4%.

将化合物3-甲氧基4-羟基苯甲醛10.0克,吡咯4.4克和N,N-二甲基甲酰600毫升加热回流2小时,冷却静止,加入200毫升蒸馏水,过滤,将粗产物用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析,即得产物四-(3-甲氧基-4-羟基)苯基卟啉3.5克。 The compound 3-methoxy-4-hydroxybenzaldehyde 10.0 g, pyrrole 4.4 g and N, N- dimethylformamide 600 ml was heated at reflux for 2 hours, cooled stationary, was added 200 ml of distilled water, filtered and the crude product with diethyl chloride as eluant to aluminum oxide as the stationary phase column chromatography to obtain the product of four - (3-methoxy-4-hydroxy) phenyl porphyrin 3.5 g. 产率26.7%。 Yield of 26.7%.

将化合物四-(3-甲氧基-4-羟基)苯基卟啉1.0克加入N-(4-溴丁基)咔唑3.0克,三乙胺2.0毫升,N,N-二甲基甲酰胺600毫升,加热搅拌反应12小时。 Compound four - (3-methoxy-4-hydroxy) phenyl porphyrin 1.0 g was added N- (4- bromobutyl) carbazole 3.0 g, 2.0 ml of triethylamine, N, N- dimethylformamide amide 600 ml, was heated with stirring for 12 hours. 产物用蒸馏水和二氯甲烷萃取,二氯甲烷萃取液浓缩,用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析即得产物四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉1.9克。 The product was extracted with distilled water and methylene chloride, methylene chloride extract was concentrated, diluted with methylene chloride as eluant alumina as the stationary phase column chromatography to obtain the product of four - [3-methoxy -4- (N - carbazole) butoxy] porphyrin 1.9 g. 产率:90.1%。 Yield: 90.1%.

将化合物四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉100毫克加入二氯化铂50毫克,乙腈600毫升,加热反应12小时。 Compound IV - [3-methoxy -4- (N- carbazole) butoxy] phenyl porphyrin was added 100 mg of platinum chloride bis 50 mg, 600 ml of acetonitrile, heated for 12 hours. 减压蒸馏蒸出乙腈,将粗产物用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析,即得产物四-[3-甲氧基-4-(N-咔唑)丁氧基]苯基卟啉铂110毫克。 Distillation under reduced pressure, acetonitrile was distilled off and the crude product using dichloromethane as eluant to aluminum oxide as the stationary phase column chromatography to obtain the product of four - [3-methoxy -4- (N- carbazole) butanoate oxy] phenyl porphyrin platinum 110 mg. 产率:98.7%。 Yield: 98.7%. 质谱分子离子峰:1876。 Mass molecular ion peak: 1876. 元素分析按化学式C112H96N8O8Pt计算:C:71.7%;H:5.2%;N:6.2%;O:6.8%实验值:C:71.8%;H:5.0%;N:6.3%;O:7.0%。 Elemental analysis is calculated according to the formula C112H96N8O8Pt: C: 71.7%; H: 5.2%; N: 6.2%; O: 6.8% Found: C: 71.8%; H: 5.0%; N: 6.3%; O: 7.0%.

实例74:化合物2-1-21的合成化合物2-1-21的合成与实例73一样。 Example 74: Synthesis of Compound 2-1-21 2-1-21 synthesis of Example 73 the same. 只是用的是1,5-二溴戊烷代替1,4-二溴丁烷。 Except that 1,5-dibromopentane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)戊氧基]苯基卟啉铂。 The product four - [3-methoxy -4- (N- carbazole) pentyloxy] phenyl porphyrin platinum. 质谱分子离子峰:1932。 Mass molecular ion peak: 1932. 元素分析按化学式C116H104N8O8Pt计算:C:72.1%;H:5.4%;N:5.8%;O:6.6%;实验值:C:71.8%;H:5.5%;N:5.5%;O:6.8%。 Elemental analysis by chemical formula C116H104N8O8Pt calculation: C: 72.1%; H: 5.4%; N: 5.8%; O: 6.6%; Found: C: 71.8%; H: 5.5%; N: 5.5%; O: 6.8%.

实例75:化合物2-1-22的合成化合物2-1-22的合成与实例73一样。 Example 75: Synthesis of Compound Synthesis Example 2-1-22 2-1-22 73 same. 只是用的是1,6-二溴己烷代替1,4-二溴丁烷。 Except that 1,6-dibromohexane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)己氧基]苯基卟啉铂。 The product four - [3-methoxy -4- (N- carbazole) hexyloxy] phenyl porphyrin platinum. 质谱分子离子峰:1988。 Mass molecular ion peak: 1988. 元素分析按化学式C120H112N8O8Pt计算:C:72.5%;H:5.7%;N:5.6%;O:6.4%;实验值:C:72.2%;H:5.5%;N:5.8%;O:6.2%。 Elemental analysis by chemical formula C120H112N8O8Pt calculation: C: 72.5%; H: 5.7%; N: 5.6%; O: 6.4%; Found: C: 72.2%; H: 5.5%; N: 5.8%; O: 6.2%.

实例76:化合物2-1-23的合成化合物2-1-23的合成与实例73一样。 Example 76: Synthesis of Compound Synthesis Example 2-1-23 2-1-23 73 same. 只是用的是1,7-二溴庚烷代替1,4-二溴丁烷。 Except that 1,7-dibromoheptane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)庚氧基]苯基卟啉铂。 The product four - [3-methoxy -4- (N- carbazole) heptyloxy] phenyl porphyrin platinum. 质谱分子离子峰:2044。 Mass molecular ion peak: 2044. 元素分析按化学式C124H120N8O8Pt计算:C:72.8%;H:5.9%;N:5.5%;O:6.3%;实验值:C:72.9%;H:6.0%;N:5.3%;O:6.4%。 Elemental analysis by chemical formula C124H120N8O8Pt calculation: C: 72.8%; H: 5.9%; N: 5.5%; O: 6.3%; Found: C: 72.9%; H: 6.0%; N: 5.3%; O: 6.4%.

实例77:化合物2-1-24的合成化合物2-1-24的合成与实例73一样。 Example 77: Synthesis of Compound Synthesis Example 2-1-24 2-1-24 73 same. 只是用的是1,8-二溴辛烷代替1,4-二溴丁烷。 Except that 1,8-dibromo-octane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)辛氧基]苯基卟啉铂。 The product four - [3-methoxy -4- (N- carbazole) octyloxy] phenyl porphyrin platinum. 质谱分子离子峰:2100。 Mass molecular ion peak: 2100. 元素分析按化学式C128H128N8O8Pt计算:C:73.2%;H:6.1%;N:5.3%;O:6.1%;实验值:C:72.9%;H:6.2%;N:5.0%;O:6.2%。 Elemental analysis by chemical formula C128H128N8O8Pt calculation: C: 73.2%; H: 6.1%; N: 5.3%; O: 6.1%; Found: C: 72.9%; H: 6.2%; N: 5.0%; O: 6.2%.

实例78:化合物2-1-25的合成化合物2-1-25的合成与实例73一样。 Example 78: Synthesis of Compound Synthesis Example 2-1-25 2-1-25 73 same. 只是用的是1,9-二溴壬烷代替1,4-二溴丁烷。 Except that 1,9-dibromo-nonane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)壬氧基]苯基卟啉铂。 The product four - [3-methoxy -4- (N- carbazole) nonyl oxy] phenyl porphyrin platinum. 质谱分子离子峰:2156。 Mass molecular ion peak: 2156. 元素分析按化学式C132H136N8O8Pt计算:C:73.5%;H:6.4%;N:5.2%;O:5.9%;实验值:C:73.8%;H:6.2%;N:5.4%;O:6.0%。 Elemental analysis by chemical formula C132H136N8O8Pt calculation: C: 73.5%; H: 6.4%; N: 5.2%; O: 5.9%; Found: C: 73.8%; H: 6.2%; N: 5.4%; O: 6.0%.

实例79:化合物2-1-26的合成化合物2-1-26的合成与实例73一样。 Example 79: Synthesis of Compound Synthesis Example 2-1-26 2-1-26 73 same. 只是用的是1,10-二溴癸烷代替1,4-二溴丁烷。 Except that the 1,10-dibromodecane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)癸氧基]苯基卟啉铂。 The product four - [3-methoxy -4- (N- carbazole) decyloxy] phenyl porphyrin platinum. 质谱分子离子峰:2212。 Mass molecular ion peak: 2212. 元素分析按化学式C136H144N8O8Pt计算:C:73.8%;H:6.6%;N:5.1%;O:5.8%;实验值:C:73.5%;H:6.8%;N:5.0%;O:6.1%。 Elemental analysis by chemical formula C136H144N8O8Pt calculation: C: 73.8%; H: 6.6%; N: 5.1%; O: 5.8%; Found: C: 73.5%; H: 6.8%; N: 5.0%; O: 6.1%.

实例80:化合物2-1-27的合成化合物2-1-27的合成与实例73一样。 Example 80: Synthesis of Compound Synthesis Example 2-1-27 2-1-27 73 same. 只是用的是1,11-二溴十一烷代替1,4-二溴丁烷。 Except that 1,11-dibromo-undecane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)十一烷氧基]苯基卟啉铂。 The product four - [3-methoxy -4- (N- carbazole) undecanoic oxy] phenyl porphyrin platinum. 质谱分子离子峰:2268。 Mass molecular ion peak: 2268. 元素分析按化学式C140H152N8O8Pt计算:C:74.1%;H:6.8%;N:4.9%;O:5.6%;实验值:C:74.4%;H:7.0%;N:5.1%;O:5.5%。 Elemental analysis by chemical formula C140H152N8O8Pt calculation: C: 74.1%; H: 6.8%; N: 4.9%; O: 5.6%; Found: C: 74.4%; H: 7.0%; N: 5.1%; O: 5.5%.

实例81:化合物2-1-28的合成化合物2-1-28的合成与实例73一样。 Example 81: Synthesis of Compound 2-1-28 2-1-28 synthesis of Example 73 the same. 只是用的是1,12-二溴十二烷代替1,4-二溴丁烷。 Except that the 1,12-dibromo dodecane instead of 1,4-dibromobutane. 产物四-[3-甲氧基-4-(N-咔唑)十二烷氧基]苯基卟啉铂。 The product four - [3-methoxy -4- (N- carbazole) dodecyloxy] phenyl porphyrin platinum. 质谱分子离子峰:2324。 Mass molecular ion peak: 2324. 元素分析按化学式C144H160N8O8Pt计算:C:74.4%;H:6.9%;N:4.8%;O:5.5%;实验值:C:74.2%;H:7.1%;N:5.1%;O:5.4%。 Elemental analysis by chemical formula C144H160N8O8Pt calculation: C: 74.4%; H: 6.9%; N: 4.8%; O: 5.5%; Found: C: 74.2%; H: 7.1%; N: 5.1%; O: 5.4%.

实例82:化合物2-1-29的合成化合物2-1-29的合成与实例73一样。 Example 82: Synthesis of Compound Synthesis Example 2-1-29 2-1-29 73 same. 只是用的是3-乙氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-ethoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-乙氧基-4-(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [3-ethoxy -4- (N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:1932。 Mass molecular ion peak: 1932. 元素分析按化学式C116H104N8O8Pt计算:C:72.1%;H:5.4%;N:5.8%;O:6.6%;实验值:C:72.4%;H:5.3%;N:5.5%;O:6.7%。 Elemental analysis by chemical formula C116H104N8O8Pt calculation: C: 72.1%; H: 5.4%; N: 5.8%; O: 6.6%; Found: C: 72.4%; H: 5.3%; N: 5.5%; O: 6.7%.

四-[3-乙氧基-4-(N-咔唑)丁氧基]苯基卟啉铂 四-[3-丙氧基-4-(N-咔唑)丁氧基]苯基卟啉铂2-1-29 2-1-30实例83:化合物2-1-30的合成化合物2-1-30的合成与实例73一样。 Four - [3-ethoxy -4- (N- carbazole) butoxy] phenyl porphyrin platinum four - [3-propoxy -4- (N- carbazole) butoxy] phenyl porphyrin porphyrin platinum 2-1-292-1-30 Example 83: Synthesis of Compound 2-1-30 2-1-30 synthesis and 73 instances of the same. 只是用的是3-丙氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-propoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-丙氧基-4-(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [3-propoxy -4- (N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:1988。 Mass molecular ion peak: 1988. 元素分析按化学式C120H112N8O8Pt计算:C:72.5%;H:5.7%;N:5.6%;O:6.4%;实验值:C:72.7%;H:5.6%;N:5.4%;O:6.1%。 Elemental analysis by chemical formula C120H112N8O8Pt calculation: C: 72.5%; H: 5.7%; N: 5.6%; O: 6.4%; Found: C: 72.7%; H: 5.6%; N: 5.4%; O: 6.1%.

实例84:化合物2-1-31的合成化合物2-1-31的合成与实例73一样。 Example 84: Synthesis of Compound 2-1-31 2-1-31 synthesis of Example 73 the same. 只是用的是3-丁氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-butoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-丁氧基-4-(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [3-butoxy--4- (N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:2044。 Mass molecular ion peak: 2044. 元素分析按化学式C124H120N8O8Pt计算:C:72.8%;H:5.9%;N:5.5%;O:6.3%;实验值:C:73.2%;H:6.0%;N:5.3%;O:6.6%。 Elemental analysis by chemical formula C124H120N8O8Pt calculation: C: 72.8%; H: 5.9%; N: 5.5%; O: 6.3%; Found: C: 73.2%; H: 6.0%; N: 5.3%; O: 6.6%.

四-[3-丁氧基-4-(N-咔唑)丁氧基]苯基卟啉铂 四-[3-叔丁氧基-4-(N-咔唑)丁氧基]苯基卟啉铂2-1-31 2-1-32实例85:化合物2-1-32的合成化合物2-1-32的合成与实例73一样。 Four - [3-butoxy--4- (N- carbazole) butoxy] phenyl porphyrin platinum four - [3-tert-butoxy -4- (N- carbazole) butoxy] phenyl porphyrin platinum 2-1-312-1-32 Example 85: Synthesis of Compound Synthesis Example 2-1-32 2-1-32 73 same. 只是用的是3-叔丁氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-tert-butoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-叔丁氧基-4-(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [3-tert-butoxy -4- (N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:2044。 Mass molecular ion peak: 2044. 元素分析按化学式C124H120N8O8Pt计算:C:72.8%;H:5.9%;N:5.5%;O:6.3%;实验值:C:73.2%;H:6.0%;N:5.3%;O:6.6%。 Elemental analysis by chemical formula C124H120N8O8Pt calculation: C: 72.8%; H: 5.9%; N: 5.5%; O: 6.3%; Found: C: 73.2%; H: 6.0%; N: 5.3%; O: 6.6%.

实例86:化合物2-1-33的合成化合物2-1-33的合成与实例73一样。 Example 86: Synthesis of Compound Synthesis Example 2-1-33 2-1-33 73 same. 只是用的是4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[4-(N-咔唑)丁氧基]苯基卟啉铂。 The product of four - [4- (N- carbazolyl) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:1756。 Mass molecular ion peak: 1756. 元素分析按化学式C108H88N8O4Pt计算:C:73.8%;H:5.1%;N:6.4%;O:3.6%;实验值:C:73.3%;H:4.9%;N:6.5%;O:3.7%。 Elemental analysis by chemical formula C108H88N8O4Pt calculation: C: 73.8%; H: 5.1%; N: 6.4%; O: 3.6%; Found: C: 73.3%; H: 4.9%; N: 6.5%; O: 3.7%.

四-[4-(N-咔唑)丁氧基]苯基卟啉铂 四-[3-(N-咔唑)丁氧基]苯基卟啉铂2-1-33 2-1-34实例87:化合物2-1-34的合成化合物2-1-34的合成与实例73一样。 Four - [4- (N- carbazolyl) butoxy] porphyrin platinum four - [3- (N- carbazolyl) butoxy] porphyrin platinum 2-1-332-1-34 Example 87: Synthesis of Compound Synthesis Example 2-1-34 2-1-34 73 same. 只是用的是3-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[3-(N-咔唑)丁氧基]苯基卟啉铂。 The product of four - [3- (N- carbazolyl) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:1756。 Mass molecular ion peak: 1756. 元素分析按化学式C108H88N8O4Pt计算:C:73.8%;H:5.1%;N:6.4%;O:3.6%;实验值:C:73.9%;H:5.1%;N:6.5%;O:3.7%。 Elemental analysis by chemical formula C108H88N8O4Pt calculation: C: 73.8%; H: 5.1%; N: 6.4%; O: 3.6%; Found: C: 73.9%; H: 5.1%; N: 6.5%; O: 3.7%.

实例88:化合物2-1-35的合成化合物2-1-35的合成与实例73一样。 Example 88: Synthesis of Compound Synthesis Example 2-1-35 2-1-35 73 same. 只是用的是3.5-二甲氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 3.5-dimethoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[2.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [2.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:1993。 Mass molecular ion peak: 1993. 元素分析按化学式C116H104N8O12Pt计算:C:69.8%;H:5.3%;N:5.6%;O:9.6%;实验值:C:70.1%;H:5.2%;N:5.4%;O:9.9%。 Elemental analysis by chemical formula C116H104N8O12Pt calculation: C: 69.8%; H: 5.3%; N: 5.6%; O: 9.6%; Found: C: 70.1%; H: 5.2%; N: 5.4%; O: 9.9%.

四-[3.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉铂 四-[2.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉铂2-1-35 2-1-36实例89:化合物2-1-36的合成化合物2-1-36的合成与实例73一样。 Four - [3.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin platinum four - [2.5-dimethoxy -4- (N- carbazole) butoxy] benzene porphyrin platinum 2-1-352-1-36 Example 89: Synthesis of Compound 2-1-36 2-1-36 synthesis and 73 instances of the same. 只是用的是2.5-二甲氧基-4-羟基苯甲醛代替3-甲氧基-4-羟基苯甲醛。 Except that 2.5-dimethoxy-4-hydroxybenzaldehyde instead of 3-methoxy-4-hydroxybenzaldehyde. 产物四-[2.5-二甲氧基-4-(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [2.5-dimethoxy -4- (N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:1993。 Mass molecular ion peak: 1993. 元素分析按化学式C116H104N8O12Pt计算:C:69.8%;H:5.3%;N:5.6%;O:9.6%;实验值:C:70.1%;H:5.2%;N:5.7%;O:9.7%。 Elemental analysis by chemical formula C116H104N8O12Pt calculation: C: 69.8%; H: 5.3%; N: 5.6%; O: 9.6%; Found: C: 70.1%; H: 5.2%; N: 5.7%; O: 9.7%.

实例90:化合物2-1-37的合成化合物2-1-37的合成与实例73一样。 Example 90: Synthesis of Compound Synthesis Example 2-1-37 2-1-37 73 same. 只是用的是3,6-二叔丁基咔唑代替咔唑。 Except that instead of 3,6-di-t-butyl-carbazole carbazole. 产物四-[3-甲氧基-4-(3,6-二叔丁基N-咔唑基)丁氧基]苯基卟啉铂。 The product four - [3-methoxy-4- (3,6-di-tert-N- carbazolyl) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:2324。 Mass molecular ion peak: 2324. 元素分析按化学式C144H160N8O8Pt计算:C:74.4%;H:6.9%;N:4.8%;O:5.5%;实验值:C:74.7%;H:7.0%;N:4.6%;O:5.7%。 Elemental analysis by chemical formula C144H160N8O8Pt calculation: C: 74.4%; H: 6.9%; N: 4.8%; O: 5.5%; Found: C: 74.7%; H: 7.0%; N: 4.6%; O: 5.7%.

四-[3-甲氧基-4-(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉铂 四-[3-甲氧基-4-(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉铂2-1-37 2-1-38实例91:化合物2-1-38的合成化合物2-1-38的合成与实例73一样。 Four - [3-methoxy-4- (3,6-di-t-butyl -N- carbazol-yl) butoxy] phenyl porphyrin platinum four - [3-methoxy-4- (1, 3,6,8-tetra-t-butyl -N- carbazolyl) butoxy] phenyl porphyrin platinum 2-1-372-1-38 Example 91: Synthesis of Compound 2-1-38 compound 2- 1-38 Example 73 Synthesis and the same. 只是用的是1,3,6,8-四叔丁基咔唑代替咔唑。 Except that in place of 1,3,6,8-tetra-tert-butyl-carbazole carbazole. 产物四-[3-甲氧基-4-(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉铂。 The product four - [3-methoxy-4- (1,3,6,8-tetra-tert-butyl -N- carbazolyl) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:2773。 Mass molecular ion peak: 2773. 元素分析按化学式C176H224N8O8Pt计算:C:76.2%;H:8.1%;N:4.0%;O:4.6%;实验值:C:76.4%;H:8.3%;N:4.1%;O:4.5%。 Elemental analysis by chemical formula C176H224N8O8Pt calculation: C: 76.2%; H: 8.1%; N: 4.0%; O: 4.6%; Found: C: 76.4%; H: 8.3%; N: 4.1%; O: 4.5%.

实例92:化合物2-2-16的合成用150毫升N,N-二甲基甲酰胺作溶剂,加入化合物氢化钠3.0克,咔唑10克和1,4-二溴丁烷20.0克,加热回流反应6小时。 Example 92: Synthesis of Compound 2-2-16 with 150 ml N, N- dimethylformamide as solvent, was added 3.0 g of sodium hydride compounds, carbazole and 10 g of 1,4-dibromo-butane 20.0 g, was heated The reaction was refluxed for 6 hours. 冷却,加入50毫升甲醇充分搅拌后过滤,收集的滤液浓缩蒸干,粗产物用环己烷为洗脱剂三氧化二铝为固定相柱层析,即得产物N-(4-溴丁基)咔唑8.2克。 After cooling, 50 ml of methanol was stirred sufficiently collected by filtration and filtrate was concentrated to dryness, the crude product was cyclohexane as eluant to aluminum oxide as the stationary phase column chromatography to give the product N- (4- bromobutyl ) carbazole 8.2 g. 产率45.4%。 Yield of 45.4%.

将化合物3.5-二甲氧基苯甲醛10.0克,吡咯4.0克和N,N-二甲基甲酰胺600毫升加热回流2小时,冷却静止,加入200毫升蒸馏水,过滤,将粗产物用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析,即得产物四-(3.5-二甲氧基)苯基卟啉2.8克。 The compound 3,5-methoxybenzaldehyde 10.0 g, pyrrole 4.0 g and N, N- dimethylformamide 600 ml was heated at reflux for 2 hours, cooled stationary, was added 200 ml of distilled water, filtered and the crude product with dichloromethane as eluant to aluminum oxide as the stationary phase column chromatography to obtain the product of four - (3,5-dimethoxyphenyl) porphyrin 2.8 g. 产率21.8%。 Yield of 21.8%.

将化合物四-(3.5-二甲氧基)苯基卟啉2.0克加入三溴化硼1毫升,甲醇100毫升,加热回流反应3小时,冷却静止,加入100毫升0.1M稀盐酸,减压蒸馏蒸干溶剂,二氯甲烷洗涤,即得产物四-(3.5-二羟基)苯基卟啉1.7克。 Compound four - (3,5-dimethoxyphenyl) porphyrin 2.0 g of boron tribromide was added 1 ml, 100 ml of methanol was heated under reflux for 3 hours, cooled stationary, dilute hydrochloric acid was added 100 ml 0.1M, vacuum distillation The solvent was evaporated, washed with methylene chloride, that was the product of four - (3,5-hydroxy) phenyl porphyrin 1.7 g. 产率98%。 98% yield.

将化合物四-(3.5-二羟基)苯基卟啉1.0克加入N-(4-溴丁基)咔唑6.0克,三乙胺2.0毫升,N,N-二甲基甲酰胺600毫升,加热搅拌反应12小时。 Compound four - (3,5-dihydroxy) phenyl porphyrin 1.0 g was added N- (4- bromobutyl) carbazole 6.0 g, 2.0 ml of triethylamine, N, N- dimethylformamide, 600 ml, was heated The reaction was stirred for 12 hours. 产物用蒸馏水和二氯甲烷萃取,二氯甲烷萃取液浓缩,用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析即得产物四-[3.5-二(N-咔唑)丁氧基]苯基卟啉2.9克。 The product was extracted with distilled water and methylene chloride, methylene chloride extract was concentrated, diluted with methylene chloride as eluant alumina as the stationary phase column chromatography to obtain the product of four - [3,5-(N- carbazole) butanoate oxy] phenyl porphyrin 2.9 g. 产率:85.6%。 Yield: 85.6%.

将化合物四-[3.5-二(N-咔唑)丁氧基]苯基卟啉100毫克加入二氯化铂50毫克,乙腈600毫升,加热回流反应12小时。 Compound IV - [3,5-(N- carbazole) butoxy] phenyl porphyrin was added 100 mg of platinum chloride bis 50 mg, 600 ml of acetonitrile was heated under reflux for 12 hours. 减压蒸馏蒸出乙腈,将粗产物用二氯甲烷为洗脱剂三氧化二铝为固定相柱层析,即得产物四-[3.5-二(N-咔唑)丁氧基]苯基卟啉铂106毫克。 Distillation under reduced pressure, acetonitrile was distilled off and the crude product using dichloromethane as eluant to aluminum oxide as the stationary phase column chromatography to obtain the product of four - [3,5-(N- carbazole) butoxy] phenyl 106 mg of porphyrin platinum. 产率:98.4%。 Yield: 98.4%. 质谱分子离子峰:2704。 Mass molecular ion peak: 2704. 元素分析按化学式C172H148N12O8Pt计算:C:76.3%;H:5.5%;N:6.2%; Elemental analysis is calculated according to the formula C172H148N12O8Pt: C: 76.3%; H: 5.5%; N: 6.2%; 四-[3.5-二(N-咔唑)丁氧基]苯基卟啉铂2-2-16O:4.7%实验值:C:75.9%;H:5.6%;N:6.4%;O:4.9%。 Four - [3.5-two (N- carbazolyl) butoxy] phenyl porphyrin platinum 2-2-16O: 4.7% Found: C: 75.9%; H: 5.6%; N: 6.4%; O: 4.9 %.

实例93:化合物2-2-17的合成化合物2-2-17的合成与实例92一样。 Example 93: Synthesis of Compound 2-2-17 2-2-17 Synthesis Example 92 of the same. 只是用的是1,5-二溴戊烷代替1,4-二溴丁烷。 Except that 1,5-dibromopentane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)戊氧基]苯基卟啉铂。 The product four - [3,5-(N- carbazole) pentyloxy] phenyl porphyrin platinum. 质谱分子离子峰:2816。 Mass molecular ion peak: 2816. 元素分析按化学式C180H164N12O8Pt计算:C:76.7%;H:5.9%;N:6.0%;O:4.5%;实验值:C:76.8%;H:6.2%;N:6.1%;O:4.7%。 Elemental analysis by chemical formula C180H164N12O8Pt calculation: C: 76.7%; H: 5.9%; N: 6.0%; O: 4.5%; Found: C: 76.8%; H: 6.2%; N: 6.1%; O: 4.7%.

实例94:化合物2-2-18的合成化合物2-2-18的合成与实例92一样。 Example 94: Synthesis of Compound 2-2-18 2-2-18 synthesis of Example 92 and the same. 只是用的是1,6-二溴己烷代替1,4-二溴丁烷。 Except that 1,6-dibromohexane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)己氧基]苯基卟啉铂。 The product four - [3,5-(N- carbazole) hexyloxy] phenyl porphyrin platinum. 质谱分子离子峰:2928。 Mass molecular ion peak: 2928. 元素分析按化学式C188H180N12O8Pt计算:C:77.1%;H:6.2%;N:5.7%;O:4.4%;实验值:C:77.2%;H:6.4%;N:6.0%;O:4.2%。 Elemental analysis by chemical formula C188H180N12O8Pt calculation: C: 77.1%; H: 6.2%; N: 5.7%; O: 4.4%; Found: C: 77.2%; H: 6.4%; N: 6.0%; O: 4.2%.

实例95:化合物2-2-19的合成化合物2-2-19的合成与实例92一样。 Example 95: Synthesis of Compound 2-2-19 2-2-19 Synthesis Example 92 of the same. 只是用的是1,7-二溴庚烷代替1,4-二溴丁烷。 Except that 1,7-dibromoheptane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)庚氧基]苯基卟啉铂。 The product four - [3,5-(N- carbazole) heptyloxy] phenyl porphyrin platinum. 质谱分子离子峰:3040。 Mass molecular ion peak: 3040. 元素分析按化学式C196H196N12O8Pt计算:C:77.4%;H:6.5%;N:5.5%;O:4.2%;实验值:C:77.2%;H:6.7%;N:5.4%:O:4.1%。 Elemental analysis by chemical formula C196H196N12O8Pt calculation: C: 77.4%; H: 6.5%; N: 5.5%; O: 4.2%; Found: C: 77.2%; H: 6.7%; N: 5.4%: O: 4.1%.

实例96:化合物2-2-20的合成化合物2-2-20的合成与实例92一样。 Example 96: Synthesis of Compound 2-2-20 2-2-20 Synthesis Example 92 of the same. 只是用的是1,8-二溴辛烷代替1,4-二溴丁烷。 Except that 1,8-dibromo-octane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)辛氧基]苯基卟啉铂。 The product of four - [3.5 two (N- carbazolyl) octyloxy] phenyl porphyrin platinum. 质谱分子离子峰:3153。 Mass molecular ion peak: 3153. 元素分析按化学式C204H212N12O8Pt计算:C:77.7%;H:6.8%;N:5.3%;O:4.1%;实验值:C:77.9%;H:7.0%;N:5.2%;O:4.2%。 Elemental analysis by chemical formula C204H212N12O8Pt calculation: C: 77.7%; H: 6.8%; N: 5.3%; O: 4.1%; Found: C: 77.9%; H: 7.0%; N: 5.2%; O: 4.2%.

实例97:化合物2-2-21的合成化合物2-2-21的合成与实例92一样。 Example 97: Synthesis of Compound 2-2-21 2-2-21 synthesis of Example 92 the same. 只是用的是1,9-二溴壬烷代替1,4-二溴丁烷。 Except that 1,9-dibromo-nonane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)壬氧基]苯基卟啉铂。 The product four - [3,5-(N- carbazole) nonyl oxy] phenyl porphyrin platinum. 质谱分子离子峰:3265。 Mass molecular ion peak: 3265. 元素分析按化学式C212H228N12O8Pt计算:C:77.9%;H:7.0%;N:5.1%;O:3.9%;实验值:C:78.1%;H:6.9%;N:5.3%;O:4.0%。 Elemental analysis by chemical formula C212H228N12O8Pt calculation: C: 77.9%; H: 7.0%; N: 5.1%; O: 3.9%; Found: C: 78.1%; H: 6.9%; N: 5.3%; O: 4.0%.

实例98:化合物2-2-22的合成化合物2-2-22的合成与实例92一样。 Example 98: Synthesis of Compound 2-2-22 2-2-22 Synthesis Example 92 of the same. 只是用的是1,10-二溴癸烷代替1,4-二溴丁烷。 Except that the 1,10-dibromodecane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)癸氧基]苯基卟啉铂。 The product four - [3,5-(N- carbazole) decyloxy] phenyl porphyrin platinum. 质谱分子离子峰:3377。 Mass molecular ion peak: 3377. 元素分析按化学式C220H244N12O8Pt计算:C:78.2%;H:7.3%;N:5.0%;O:3.8%;实验值:C:78.5%;H:7.1%;N:5.2%;O:3.7%。 Elemental analysis by chemical formula C220H244N12O8Pt calculation: C: 78.2%; H: 7.3%; N: 5.0%; O: 3.8%; Found: C: 78.5%; H: 7.1%; N: 5.2%; O: 3.7%.

实例99:化合物2-2-23的合成化合物2-2-23的合成与实例92一样。 Example 99: Synthesis of Compound 2-2-23 2-2-23 Synthesis Example 92 of the same. 只是用的是1,11-二溴十一烷代替1,4-二溴丁烷。 Except that 1,11-dibromo-undecane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)十一烷氧基]苯基卟啉铂。 The product four - [3,5-(N- carbazole) undecanoic oxy] phenyl porphyrin platinum. 质谱分子离子峰:3489。 Mass molecular ion peak: 3489. 元素分析按化学式C228H260N12O8Pt计算:C:78.4%;H:7.5%;N:4.8%;O:3.7%;实验值:C:78.2%;H:7.3%;N:5.0%;O:3.8%。 Elemental analysis by chemical formula C228H260N12O8Pt calculation: C: 78.4%; H: 7.5%; N: 4.8%; O: 3.7%; Found: C: 78.2%; H: 7.3%; N: 5.0%; O: 3.8%.

实例100:化合物2-2-24的合成化合物2-2-24的合成与实例92一样。 Examples 100: Synthesis of Compound Synthesis Example 2-2-24 2-2-24 92 of the same. 只是用的是1,12-二溴十二烷代替1,4-二溴丁烷。 Except that the 1,12-dibromo dodecane instead of 1,4-dibromobutane. 产物四-[3.5-二(N-咔唑)十二烷氧基]苯基卟啉铂。 The product four - [3,5-(N- carbazole) dodecyloxy] phenyl porphyrin platinum. 质谱分子离子峰:3601。 Mass molecular ion peak: 3601. 元素分析按化学式C236H276N12O8Pt计算:C:78.7%;H:7.7%;N:4.7%;O:3.6%;实验值:C:79.2%;H:7.6%;N:4.6%;O:3.8%。 Elemental analysis by chemical formula C236H276N12O8Pt calculation: C: 78.7%; H: 7.7%; N: 4.7%; O: 3.6%; Found: C: 79.2%; H: 7.6%; N: 4.6%; O: 3.8%.

四-[3.4-二(N-咔唑)丁氧基]苯基卟啉铂 四-[2.5-二(N-咔唑)丁氧基]苯基卟啉铂2-2-25 2-2-26 Four - [3.4-two (N- carbazole) butoxy] phenyl porphyrin platinum four - [2,5-di (N- carbazole) butoxy] phenyl porphyrin platinum 2-2-252-2 -26

实例101:化合物2-2-25的合成化合物2-2-25的合成的合成与实例92一样。 Example 101: Synthesis of compounds Synthesis of Compound 2-2-25 2-2-25 Synthesis Example 92 of the same. 只是用的是3.4-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 3,4-dimethoxybenzaldehyde in place of 3,5-dimethoxybenzaldehyde. 产物四-[3.4-二(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [3.4 two (N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:2704。 Mass molecular ion peak: 2704. 元素分析按化学式C172H148N12O8Pt计算:C:76.3%;H:5.5%;N:6.2%;O:4.7%实验值:C:76.0%;H:5.6%;N:6.4%;O:4.5%。 Elemental analysis is calculated according to the formula C172H148N12O8Pt: C: 76.3%; H: 5.5%; N: 6.2%; O: 4.7% Found: C: 76.0%; H: 5.6%; N: 6.4%; O: 4.5%.

实例102:化合物2-2-26的合成化合物2-2-26的合成与实例92一样。 Example 102: Synthesis of Compound 2-2-26 2-2-26 Synthesis Example 92 of the same. 只是用的是2.5-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2,5-dimethyl-methoxybenzaldehyde instead of 3,5-dimethoxybenzaldehyde. 产物四-[2.5-二(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [2,5-dimethyl (N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:2704。 Mass molecular ion peak: 2704. 元素分析按化学式C172H148N12O8Pt计算:C:76.3%;H:5.5%;N:6.2%;O:4.7%实验值:C:75.9%;H:5.6%;N:6.1%;O:4.9%。 Elemental analysis is calculated according to the formula C172H148N12O8Pt: C: 76.3%; H: 5.5%; N: 6.2%; O: 4.7% Found: C: 75.9%; H: 5.6%; N: 6.1%; O: 4.9%.

实例103:化合物2-2-27的合成化合物2-2-27的合成的合成与实例92一样。 Example 103: Synthesis of Compound Synthesis Synthesis of Compound 2-2-27 2-2-27 Example 92 the same. 只是用的是2.4-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2,4-dimethoxybenzaldehyde in place of 3,5-dimethoxybenzaldehyde. 产物四-[2.4-二(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [2.4-(N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:2704。 Mass molecular ion peak: 2704. 元素分析按化学式C172H148N12O8Pt计算:C:76.3%;H:5.5%;N:6.2%;O:4.7%实验值:C:75.9%;H:5.6%;N:6.4%;O:4.8%。 Elemental analysis is calculated according to the formula C172H148N12O8Pt: C: 76.3%; H: 5.5%; N: 6.2%; O: 4.7% Found: C: 75.9%; H: 5.6%; N: 6.4%; O: 4.8%.

实例104:化合物2-2-28的合成化合物2-2-28的合成与实例92一样。 Example 104: Synthesis of Compound 2-2-28 2-2-28 synthesis of Example 92 the same. 只是用的是2.6-二甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2,6-dimethoxybenzaldehyde in place of 3,5-dimethoxybenzaldehyde. 产物四-[2.6-二(N-咔唑)丁氧基]苯基卟啉铂。 The product four - [2,6-two (N- carbazole) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:2704。 Mass molecular ion peak: 2704. 元素分析按化学式C172H148N12O8Pt计算:C:76.3%;H:5.5%;N:6.2%;O:4.7%实验值:C:76.5%;H:5.3%;N:6.4%;O:4.9%。 Elemental analysis is calculated according to the formula C172H148N12O8Pt: C: 76.3%; H: 5.5%; N: 6.2%; O: 4.7% Found: C: 76.5%; H: 5.3%; N: 6.4%; O: 4.9%.

四-[2.4-二(N-咔唑)丁氧基]苯基卟啉铂 四-[2.6-二(N-咔唑)丁氧基]苯基卟啉铂2-2-27 2-2-28实例105:化合物2-2-29的合成化合物2-2-29的合成与实例92一样。 Four - [2.4-(N- carbazole) butoxy] phenyl porphyrin platinum four - [2,6-two (N- carbazole) butoxy] phenyl porphyrin platinum 2-2-272-2 -28 Example 105: Synthesis of Compound 2-2-29 compound 2-2-29 of Synthesis Example 92 of the same. 只是用的是3,6-二叔丁基咔唑代替咔唑。 Except that instead of 3,6-di-t-butyl-carbazole carbazole. 产物四-[3,5-二(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉铂。 The product four - [3,5-bis (3,6-di-tert--N- carbazolyl) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:3601。 Mass molecular ion peak: 3601. 元素分析按化学式C236H276N12O8Pt计算:C:78.7%;H:7.7%;N:4.7%;O:3.6%实验值:C:79.0%;H:7.5%;N:4.6%;O:3.8%。 Elemental analysis is calculated according to the formula C236H276N12O8Pt: C: 78.7%; H: 7.7%; N: 4.7%; O: 3.6% Found: C: 79.0%; H: 7.5%; N: 4.6%; O: 3.8%.

实例106:化合物2-2-30的合成化合物2-2-30的合成与实例92一样。 Example 106: Synthesis of Compound 2-2-30 2-2-30 Synthesis Example 92 of the same. 只是用的是1,3,6,8-四叔丁基咔唑代替咔唑。 Except that in place of 1,3,6,8-tetra-tert-butyl-carbazole carbazole. 产物四-[3,5-二(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉铂。 The product four - [3,5-bis (1,3,6,8-tetra-butyl -N- carbazolyl) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:4498。 Mass molecular ion peak: 4498. 元素分析按化学式C300H404N12O8Pt计算:C:80.0%;H:9.1%;N:3.7%;O:2.8%实验值:C:80.3%;H:9.0%;N:3.9%:O:3.0%。 Elemental analysis is calculated according to the formula C300H404N12O8Pt: C: 80.0%; H: 9.1%; N: 3.7%; O: 2.8% Found: C: 80.3%; H: 9.0%; N: 3.9%: O: 3.0%.

四-[3.5-二(3,6-二叔丁基-N-咔唑基)丁氧基]苯基卟啉铂 四-[3.5-二(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉铂2-2-29 2-2-30实例107:化合物2-3-03的合成化合物2-3-03的合成与实例92一样。 Four - [3.5-bis (3,6-di-t-butyl -N- carbazol-yl) butoxy] phenyl porphyrin platinum four - [3.5-bis (1,3,6,8-tetra-tert-butyl -N- carbazol-yl) butoxy] phenyl porphyrin platinum 2-2-292-2-30 Example 107: Synthesis of Compound 2-3-03 2-3-03 Synthesis Example 92 of the same. 只是用的是2.4.6-三甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that 2.4.6- three-methoxybenzaldehyde instead of 3,5-dimethoxybenzaldehyde. 产物四-[2.4.6-三(N-咔唑)丁氧基]苯基卟啉铂。 The product of four - [2.4.6- three (N- carbazolyl) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:3653。 Mass molecular ion peak: 3653. 元素分析按化学式C236H208N16O12Pt计算:C:77.5%;H:5.7%;N:6.1%;O:5.3%实验值:C:77.3%;H:5.8%;N:6.3%;O:5.2%。 Elemental analysis is calculated according to the formula C236H208N16O12Pt: C: 77.5%; H: 5.7%; N: 6.1%; O: 5.3% Found: C: 77.3%; H: 5.8%; N: 6.3%; O: 5.2%.

实例108:化合物2-3-04的合成化合物2-3-04的合成与实例92一样。 Example 108: Synthesis of Compound 2-3-04 2-3-04 Synthesis Example 92 of the same. 只是用的是1,3,6,8-四叔丁基咔唑代替咔唑,2.4.6-三甲氧基苯甲醛代替3.5-二甲氧基苯甲醛。 Except that in place of 1,3,6,8-tetra-t-butyl-carbazole carbazole, 2.4.6- three-methoxybenzaldehyde instead of 3,5-dimethoxybenzaldehyde. 产物四-[2.4.6-三(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉铂。 The product four - [2.4.6- tri (1,3,6,8-tetra-tert-butyl -N- carbazol-yl) butoxy] phenyl porphyrin platinum. 质谱分子离子峰:6344。 Mass molecular ion peak: 6344. 元素分析按化学式C428H592N16O12Pt计算:C:81.0%;H:9.4%;N:3.5%;O:3.0%实验值:C:81.2%:H:9.3%;N:3.6%;O:3.1%。 Elemental analysis is calculated according to the formula C428H592N16O12Pt: C: 81.0%; H: 9.4%; N: 3.5%; O: 3.0% Found: C: 81.2%: H: 9.3%; N: 3.6%; O: 3.1%.

四-[2.4.6-三(N-咔唑)丁氧基]苯基卟啉铂 四-[2.4.6-三(1,3,6,8-四叔丁基-N-咔唑基)丁氧基]苯基卟啉铂2-3-03 2-3-04实例109:以化合物1-1-01为发光层的发光器件发光器件结构为[ITO/PEDOT/1-1-01:ADS129/Ba/Al],发光材料1-1-01在ADS129中的掺杂浓度为4wt%,器件的开启电压在6.5V左右,最大亮度达到100cd/m2,最大外量子效率0.14%。 Four - [2.4.6- three (N- carbazole) butoxy] phenyl porphyrin platinum four - [2.4.6- tri (1,3,6,8-tetra-tert-butyl -N- carbazolyl ) butoxy] phenyl porphyrin platinum 2-3-032-3-04 Example 109: In the light emitting layer, the compound 1-1-01 as a light emitting device structure for a light emitting device [ITO / PEDOT / 1-1-01 : ADS129 / Ba / Al], the luminescent material 1-1-01 ADS129 in doping concentration is 4wt%, turn-on voltage of the device is about 6.5V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 0.14%. 器件的发光峰位在663.4nm,为红色发光。 Emission peak position of the device in 663.4nm, red light.

实例110:以化合物1-1-19为发光层的发光器件发光器件结构为[ITO/PEDOT/1-1-19:ADS129/Ba/Al],发光材料1-1-19在ADS129中的掺杂浓度为4wt%,器件的开启电压在6.0V左右,最大亮度达到100cd/m2,最大外量子效率0.15%。 Example 110: In the light emitting layer, the compound 1-1-19 as a light emitting device structure for a light emitting device [ITO / PEDOT / 1-1-19: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 1-1-19 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 6.0V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 0.15%. 器件的发光峰位在663.8nm,为红色发光。 Emission peak position of the device in 663.8nm, red light.

实例111:以化合物1-2-01为发光层的发光器件发光器件结构为[ITO/PEDOT/1-2-01:ADS129/Ba/Al],发光材料1-2-01在ADS129中的掺杂浓度为4wt%,器件的开启电压在6.5V左右,最大亮度达到100cd/m2,最大外量子效率0.12%。 Example 111: In the light emitting layer, the compound 1-2-01 as a light emitting device structure for a light emitting device [ITO / PEDOT / 1-2-01: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 1-2-01 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 6.5V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 0.12%. 器件的发光峰位在662.5nm,为红色发光。 Emission peak position of the device in 662.5nm, red light.

实例112:以化合物1-2-15为发光层的发光器件发光器件结构为[ITO/PEDOT/1-2-15:ADS129/Ba/Al],发光材料1-2-15在ADS129中的掺杂浓度为4wt%,器件的开启电压在6.8V左右,最大亮度达到100cd/m2,最大外量子效率0.13%。 Example 112: In the light emitting layer, the compound 1-2-15 as a light emitting device structure for a light emitting device [ITO / PEDOT / 1-2-15: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 1-2-15 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 6.8V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 0.13%. 器件的发光峰位在665.1nm,为红色发光。 Emission peak position of the device in 665.1nm, red light.

实例113:以化合物1-3-01为发光层的发光器件发光器件结构为[ITO/PEDOT/1-3-01:ADS129/Ba/Al],发光材料1-3-01在ADS129中的掺杂浓度为4wt%,器件的开启电压在6.7V左右,最大亮度达到100cd/m2,最大外量子效率0.15%。 Examples 113: the compound 1-3-01 as a light emitting layer, a light emitting device structure for a light emitting device [ITO / PEDOT / 1-3-01: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 1-3-01 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 6.7V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 0.15%. 器件的发光峰位在663.5nm,为红色发光。 Emission peak position of the device in 663.5nm, red light.

实例114:以化合物1-3-02为发光层的发光器件发光器件结构为[ITO/PEDOT/1-3-02:ADS129/Ba/Al],发光材料1-3-02在ADS129中的掺杂浓度为4wt%,器件的开启电压在6.6V左右,最大亮度达到100cd/m2,最大外量子效率0.15%。 Example 114: In the light emitting layer, the compound 1-3-02 as a light emitting device structure for a light emitting device [ITO / PEDOT / 1-3-02: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 1-3-02 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 6.6V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 0.15%. 器件的发光峰位在665.0nm,为红色发光。 Emission peak position of the device in 665.0nm, red light.

实例115:以化合物2-1-01为发光层的发光器件发光器件结构为[ITO/PEDOT/2-1-01:ADS129/Ba/Al],发光材料2-1-01在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.5V左右,最大亮度达到240cd/m2,最大外量子效率0.27%。 Example 115: In the light emitting layer, the compound 2-1-01 as a light emitting device structure for a light emitting device [ITO / PEDOT / 2-1-01: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 2-1-01 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 8.5V, the maximum brightness of 240cd / m2, the maximum external quantum efficiency of 0.27%. 器件的发光峰位在607.6nm,为红色发光。 Emission peak position of the device in 607.6nm, red light.

实例116:以化合物2-1-19为发光层的发光器件发光器件结构为[ITO/PEDOT/2-1-19:ADS129/Ba/Al],发光材料2-1-19在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.0V左右,最大亮度达到240cd/m2,最大外量子效率0.27%。 Examples 116: the compound 2-1-19 as a light emitting layer, a light emitting device structure for a light emitting device [ITO / PEDOT / 2-1-19: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 2-1-19 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 8.0V, the maximum brightness of 240cd / m2, the maximum external quantum efficiency of 0.27%. 器件的发光峰位在608.6nm,为红色发光。 Emission peak position of the device in 608.6nm, red light.

实例117:以化合物2-2-01为发光层的发光器件发光器件结构为[ITO/PEDOT/2-2-01:ADS129/Ba/Al],发光材料2-2-01在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.2V左右,最大亮度达到230cd/m2,最大外量子效率0.25%。 Example 117: In the light emitting layer, the compound 2-2-01 as a light emitting device structure for a light emitting device [ITO / PEDOT / 2-2-01: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 2-2-01 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 8.2V, the maximum brightness of 230cd / m2, the maximum external quantum efficiency of 0.25%. 器件的发光峰位在607.6nm,为红色发光。 Emission peak position of the device in 607.6nm, red light.

实例118:以化合物2-2-15为发光层的发光器件发光器件结构为[ITO/PEDOT/2-2-15:ADS129/Ba/Al],发光材料2-2-15在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.5V左右,最大亮度达到240cd/m2,最大外量子效率0.28%。 Example 118: In the light emitting layer, the compound 2-2-15 as a light emitting device structure for a light emitting device [ITO / PEDOT / 2-2-15: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 2-2-15 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 8.5V, the maximum brightness of 240cd / m2, the maximum external quantum efficiency of 0.28%. 器件的发光峰位在604.2nm,为红色发光。 Emission peak position of the device in 604.2nm, red light.

实例119:以化合物2-3-01为发光层的发光器件发光器件结构为[ITO/PEDOT/2-3-01:ADS129/Ba/Al],发光材料2-3-01在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.0V左右,最大亮度达到260cd/m2,最大外量子效率0.26%。 Examples 119: the compound 2-3-01 as a light emitting layer, a light emitting device structure for a light emitting device [ITO / PEDOT / 2-3-01: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 2-3-01 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 8.0V, the maximum brightness of 260cd / m2, the maximum external quantum efficiency of 0.26%. 器件的发光峰位在607.2nm,为红色发光。 Emission peak position of the device in 607.2nm, red light.

实例120:以化合物2-3-02为发光层的发光器件发光器件结构为[ITO/PEDOT/2-3-02:ADS129/Ba/Al],发光材料2-3-02在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.9V左右,最大亮度达到220cd/m2,最大外量子效率0.29%。 Example 120: In the light emitting layer, the compound 2-3-02 as a light emitting device structure for a light emitting device [ITO / PEDOT / 2-3-02: ADS129 / Ba / Al], the luminescent material incorporated in ADS129 of 2-3-02 heteroaryl concentration of 4wt%, the threshold voltage of the device is about 8.9V, the maximum brightness of 220cd / m2, the maximum external quantum efficiency of 0.29%. 器件的发光峰位在606.5nm,为红色发光。 Emission peak position of the device in 606.5nm, red light.

实例121:以化合物2-1-20为发光层的发光器件(A)发光器件结构为[ITO/PEDOT/PVK/2-1-20:ADS129/Ba/Al],发光材料2-1-20在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.5V左右,最大亮度达到70cd/m2,最大外量子效率1.4%。 Example 121: In the compound 2-1-20 as a light emitting layer, the light emitting device (A) of the light emitting device structure of [ITO / PEDOT / PVK / 2-1-20: ADS129 / Ba / Al], the luminescent material 2-1-20 The doping concentration ADS129 was 4wt%, turn-on voltage of the device is about 8.5V, the maximum brightness of 70cd / m2, the maximum external quantum efficiency of 1.4%. 器件的发光峰位在682.8nm,为红色发光。 Emission peak position of the device in 682.8nm, red light.

实例122:以化合物2-1-20为发光层的发光器件(B)发光器件结构为[ITO/PEDOT/PVK/2-1-20:ADS129:PBD/Ba/Al],发光材料2-1-20在ADS129中的掺杂浓度为4wt%,空穴阻挡材料PBD在ADS129中的掺杂浓度为30wt%,器件的开启电压在4.5V左右,最大亮度达到100cd/m2,最大外量子效率5.68%。 Examples 122: the compound 2-1-20 as a light emitting device (B) light emitting layer of the light emitting device structure of [ITO / PEDOT / PVK / 2-1-20: ADS129: PBD / Ba / Al], luminescent materials 2-1 ADS129 -20 doping concentration in the range of 4wt%, the hole blocking material in ADS129 PBD doping concentration in the range of 30wt%, the threshold voltage of the device is about 4.5V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 5.68 %. 器件的发光峰位在675.2nm,为红色发光。 Emission peak position of the device in 675.2nm, red light.

实例123:以化合物2-1-38为发光层的发光器件(A)发光器件结构为[ITO/PEDOT/PVK/2-1-38:ADS129/Ba/Al],发光材料2-1-38在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.4V左右,最大亮度达到75cd/m2,最大外量子效率1.3%。 Example 123: In the compound 2-1-38 as a light emitting layer, the light emitting device (A) of the light emitting device structure of [ITO / PEDOT / PVK / 2-1-38: ADS129 / Ba / Al], the luminescent material 2-1-38 The doping concentration ADS129 was 4wt%, turn-on voltage of the device is about 8.4V, the maximum brightness of 75cd / m2, the maximum external quantum efficiency of 1.3%. 器件的发光峰位在682.8nm,为红色发光。 Emission peak position of the device in 682.8nm, red light.

实例124:以化合物2-1-38为发光层的发光器件(B)发光器件结构为[ITO/PEDOT/PVK/2-1-38:ADS129:PBD/Ba/Al],发光材料2-1-20在ADS129中的掺杂浓度为4wt%,空穴阻挡材料PBD在ADS129中的掺杂浓度为30wt%,器件的开启电压在4.0V左右,最大亮度达到100cd/m2,最大外量子效率5.60%。 Example 124: In the compound 2-1-38 as a light emitting device (B) light emitting layer of the light emitting device structure of [ITO / PEDOT / PVK / 2-1-38: ADS129: PBD / Ba / Al], luminescent materials 2-1 ADS129 -20 doping concentration in the range of 4wt%, the hole blocking material in ADS129 PBD doping concentration in the range of 30wt%, the threshold voltage of the device is about 4.0V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 5.60 %. 器件的发光峰位在675.2nm,为红色发光。 Emission peak position of the device in 675.2nm, red light.

实例125:以化合物2-2-16为发光层的发光器件(A)发光器件结构为[ITO/PEDOT/PVK/2-2-16:ADS129/Ba/Al],发光材料2-2-16在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.8V左右,最大亮度达到70cd/m2,最大外量子效率1.2%。 Examples 125: the compound 2-2-16 as a light emitting layer, the light emitting device (A) of the light emitting device structure of [ITO / PEDOT / PVK / 2-2-16: ADS129 / Ba / Al], the luminescent material 2-2-16 The doping concentration ADS129 was 4wt%, turn-on voltage of the device is about 8.8V, the maximum brightness of 70cd / m2, the maximum external quantum efficiency of 1.2%. 器件的发光峰位在682.0nm,为红色发光。 Emission peak position of the device in 682.0nm, red light.

实例126:以化合物2-2-16为发光层的发光器件(B)发光器件结构为[ITO/PEDOT/PVK/2-2-16:ADS129:PBD/Ba/Al],发光材料2-2-16在ADS129中的掺杂浓度为4wt%,空穴阻挡材料PBD在ADS129中的掺杂浓度为30wt%,器件的开启电压在4.5V左右,最大亮度达到100cd/m2,最大外量子效率5.5%。 Example 126: In the compound 2-2-16 as a light emitting device (B) light emitting layer of the light emitting device structure of [ITO / PEDOT / PVK / 2-2-16: ADS129: PBD / Ba / Al], luminescent materials 2-2 -16 ADS129 doping concentration in the range of 4wt%, the hole blocking material in ADS129 PBD doping concentration in the range of 30wt%, the threshold voltage of the device is about 4.5V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 5.5 %. 器件的发光峰位在675.5nm,为红色发光。 Emission peak position of the device in 675.5nm, red light.

实例127:以化合物2-2-30为发光层的发光器件(A)发光器件结构为[ITO/PEDOT/PVK/2-1-20:ADS129/Ba/Al],发光材料2-2-30在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.5V左右,最大亮度达到70cd/m2,最大外量子效率1.4%。 Example 127: In the compound 2-2-30 as a light emitting layer, the light emitting device (A) of the light emitting device structure of [ITO / PEDOT / PVK / 2-1-20: ADS129 / Ba / Al], the luminescent material 2-2-30 The doping concentration ADS129 was 4wt%, turn-on voltage of the device is about 8.5V, the maximum brightness of 70cd / m2, the maximum external quantum efficiency of 1.4%. 器件的发光峰位在682.8nm,为红色发光。 Emission peak position of the device in 682.8nm, red light.

实例128:以化合物2-2-30为发光层的发光器件(B)发光器件结构为[ITO/PEDOT/PVK/2-2-30:ADS129:PBD/Ba/Al],发光材料2-2-30在ADS129中的掺杂浓度为4wt%,空穴阻挡材料PBD在ADS129中的掺杂浓度为30wt%,器件的开启电压在4.5V左右,最大亮度达到100cd/m2,最大外量子效率5.68%。 Example 128: In the compound 2-2-30 as a light emitting device (B) light emitting layer of the light emitting device structure of [ITO / PEDOT / PVK / 2-2-30: ADS129: PBD / Ba / Al], luminescent materials 2-2 ADS129 -30 doping concentration in the range of 4wt%, the hole blocking material in ADS129 PBD doping concentration in the range of 30wt%, the threshold voltage of the device is about 4.5V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 5.68 %. 器件的发光峰位在676.2nm,为红色发光。 Emission peak position of the device in 676.2nm, red light.

实例129:以化合物2-3-03为发光层的发光器件(A)发光器件结构为[ITO/PEDOT/PVK/2-3-03:ADS129/Ba/Al],发光材料2-3-03在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.0V左右,最大亮度达到60cd/m2,最大外量子效率1.2%。 Example 129: In the compound 2-3-03 as a light emitting layer, the light emitting device (A) of the light emitting device structure of [ITO / PEDOT / PVK / 2-3-03: ADS129 / Ba / Al], the luminescent material 2-3-03 The doping concentration ADS129 was 4wt%, turn-on voltage of the device is about 8.0V, the maximum brightness of 60cd / m2, the maximum external quantum efficiency of 1.2%. 器件的发光峰位在681.8nm,为红色发光。 Emission peak position of the device in 681.8nm, red light.

实例130:以化合物2-3-03为发光层的发光器件(B)发光器件结构为[ITO/PEDOT/PVK/2-3-03:ADS129:PBD/Ba/Al],发光材料2-3-03在ADS129中的掺杂浓度为4wt%,空穴阻挡材料PBD在ADS129中的掺杂浓度为30wt%,器件的开启电压在4.0V左右,最大亮度达到110cd/m2,最大外量子效率5.75%。 Examples 130: the compound 2-3-03 as a light emitting device (B) light emitting layer of the light emitting device structure of [ITO / PEDOT / PVK / 2-3-03: ADS129: PBD / Ba / Al], luminescent materials 2-3 -03 ADS129 doping concentration in the range of 4wt%, the hole blocking material in ADS129 PBD doping concentration in the range of 30wt%, the threshold voltage of the device is about 4.0V, the maximum brightness of 110cd / m2, the maximum external quantum efficiency of 5.75 %. 器件的发光峰位在675.0nm,为红色发光。 Emission peak position of the device in 675.0nm, red light.

实例131:以化合物2-3-04为发光层的发光器件(A)发光器件结构为[ITO/PEDOT/PVK/2-3-04:ADS129/Ba/Al],发光材料2-3-04在ADS129中的掺杂浓度为4wt%,器件的开启电压在8.5V左右,最大亮度达到72cd/m2,最大外量子效率1.6%。 Example 131: In the compound 2-3-04 as a light emitting layer, the light emitting device (A) of the light emitting device structure of [ITO / PEDOT / PVK / 2-3-04: ADS129 / Ba / Al], the luminescent material 2-3-04 The doping concentration ADS129 was 4wt%, turn-on voltage of the device is about 8.5V, the maximum brightness of 72cd / m2, the maximum external quantum efficiency of 1.6%. 器件的发光峰位在684.0nm,为红色发光。 Emission peak position of the device in 684.0nm, red light.

实例132 :以化合物2-3-04为发光层的发光器件(B)发光器件结构为[ITO/PEDOT/PVK/2-3-04:ADS129:PBD/Ba/Al],发光材料2-3-04在ADS129中的掺杂浓度为4wt%,空穴阻挡材料PBD在ADS129中的掺杂浓度为30wt%,器件的开启电压在4.4V左右,最大亮度达到100cd/m2,最大外量子效率5.66%。 Examples 132: the compound 2-3-04 as a light emitting device (B) light emitting layer of the light emitting device structure of [ITO / PEDOT / PVK / 2-3-04: ADS129: PBD / Ba / Al], luminescent materials 2-3 -04 ADS129 doping concentration in the range of 4wt%, the hole blocking material in ADS129 PBD doping concentration in the range of 30wt%, the threshold voltage of the device is about 4.4V, the maximum brightness of 100cd / m2, the maximum external quantum efficiency of 5.66 %. 器件的发光峰位在675.5nm,为红色发光。 Emission peak position of the device in 675.5nm, red light.

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