WO2010112452A1

WO2010112452A1 - Oligocondensed perylene bisimides

Info

Publication number: WO2010112452A1
Application number: PCT/EP2010/054079
Authority: WO
Inventors: Jianqiang Qu; Zhaohui Wang; Hualei Qian
Original assignee: Basf Se; Institute Of Chemistry, Chinese Academy Of Science; Zhen, Yonggang
Priority date: 2009-03-30
Filing date: 2010-03-29
Publication date: 2010-10-07
Also published as: WO2010112452A9; WO2010111822A1

Abstract

The present invention relates to oligocondensed perylene bisimides, a method for their production and their use.

Description

OLIGOCONDENSED PERYLENE BISIMIDES

BACKGROUND OF THE INVENTION

DESCRIPTION OF THE RELATED ART

It is expected that, in the future, "organic electronics" will be one of the most important technical fields for the development of new materials. These include inter alia organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), and photovoltaics. Great potential for development is ascribed to organic field-effect transistors, for example in memory elements and integrated optoelectronic devices. Organic light-emitting diodes (OLEDs) exploit the property of materials of emitting light when they are excited by electrical current. OLEDs are particularly of interest as alternatives to cathode ray tubes and liquid-crystal displays for producing flat visual display units. There is also a need for effective dyes that are useful for solar energy harvesting and can be employed e.g. in dye sensitized solar cells. Great potential for development is also ascribed to materials which have maximum transport widths and high mobilities for light-induced excited states (high exciton diffusion lengths) and which are thus advantageously suitable for use as an active material in so-called excitonic solar cells. There is a continuous need for novel compounds with advantageous performance properties which serve as a feedstock for organic electronics, as a dye, photosensitive compound, etc.

H. Langhals and P. Blanke describe in Dyes and Pigments 2003, 59, pages 109-1 16, perylene bisimides of the formulae

R R wherein R is CH(C₆Hi₃)₂,

or CH(CHs)₂ and their use as near infrared (NIR) dyes. H. Langhals and S. Kirner disclose in Eur. J. Org. Chem. 2000, pages 365-380, core extended perylene bisimides that are fluorescent dyes and can be employed inter alia as sensitizer in Grazel solar cells:

H. Quian, C. Liu, Z. Wang and D. Zhu describe in Chem. Commun., 2006, pages 4587- 4589, S-heterocyclic annulated perylene bisimides

H. Quian, Z. Wang, W. Yue and D. Zhu describe in J. Am. Chem. Soc. 2007, 129, pages 10664-10665, a one-pot synthesis of triply linked diperylene bisimides of the general formula

where X is hydrogen or chlorine by combination of Ullmann reaction and C-H transformation.

Perylene bisimides with strained hetero rings in the bay region are of potential interest in view of their optical and electrochemical properties. The inventors have found that it is not possible to synthesize compound B) by the Buchwald-Hartwig reaction of tetrahalogen-substituted perylene-3,4:9,10-tetracarboxylbisimides A) with an amine R¹-NH2. Instead, only compound C) is observed.

(C) Surprisingly, it was also found that oligocondensed perylene bisimides with strained pyrrole-rings in the bay region can be synthesized by the Buchwald-Hartwig reaction. SUMMARY OF THE INVENTION

In a first aspect, the invention provides oligocondensed perylene bisimides, comprising two outer moieties of the formula Ia

(Ia) or one outer moiety of the formula Ia and one outer moiety of the formula Ib

and n inner moieties selected from moieties of the formulae (Ic) and (Id)

where

# is the site of attachment to a corresponding site of attachment of a moiety Ia, Ib, Ic or Id,

R^a are each identical or different radicals, selected from hydrogen and unsubstituted or substituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or hetaryl,

R^b are each identical or different radicals, selected from hydrogen and unsubstituted or substituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or hetaryl,

n is an integer from O to 6,

R¹ is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl or polycyclyl,

or

two substituents R¹ form a divalent bridging group X between two moieties of the formula Ia, wherein X has from 1 to 20 bridge atoms between the flanking bonds, and

R² and R³ are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl or halogen.

In a further aspect, the invention provides a method for producing oligocondensed perylene bisimides. In a further aspect the invention relates to compositions of oligocondensed perylene bisimides obtainable by the afore-mentioned method.

The present invention further relates to the use of the oligocondensed perylene bisimides for coloring high molecular weight organic and inorganic materials, as materials which absorb IR laser beams in the fusion treatment of plastics parts, for preparing aqueous polymer dispersions which absorb in the near infrared region of the electromagnetic spectrum, for obtaining markings and inscriptions which absorb infrared light but are invisible to the human eye, as infrared absorbers for heat management, and as active components in photovoltaics.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the UV/VIS spectrum of the compound (31 )

FIG. 2 shows the UV/VIS spectra of the following compounds A and B (intermediates)

FIG.3 shows the UV/VIS spectra of the compounds (22), (28), (31) and intermediate C

(C)

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION

The oligocondensed perylene bisimides of the invention have the following structural concept.

The outer moieties and, if present, the inner moieties are triply linked, i.e. each two moieties are linked by three covalent carbon-carbon single bonds. Scheme 1 shows a diperylene bisimide formed from one moiety Ia and one moiety Ib.

Scheme 1 :

In the oligocondensed perylene bisimides, n+2 is the number of perylene units which are triply linked in the bay region and form the basic skeleton of the inventive compounds. Scheme 2 shows examples of oligocondensed perylene bisimides with 2, 3 and 4 perylene units (n = 0, 1 and 2):

Scheme 2:

n = 0

n = 1

n = 2

The oligocondensed perylene bisimides according to the invention can comprise two outer moieties of the formula Ia or one outer moiety of the formula Ia and one outer moiety of the formula 1 b (see scheme 3).

Scheme 3:

The oligocondensed perylene bisimides according to the invention can be present in form of isomers. Scheme 4 shows an example of constitutional isomers of oligocondensed perylene bisimides with three perylene units.

Scheme 4:

Scheme 5 shows an example of stereoisomers of oligocondensed perylene bisimides with three perylene units.

Scheme 5:

For the purposes of the present invention, the term "alkyl" embraces straight-chain and branched alkyl groups. These groups are preferably straight-chain or branched C1-C30- alkyl groups, more preferably Ci-C2o-alkyl groups, particularly preferably Ci-Ci2-alkyl groups. Examples of alkyl groups are, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.

The expression "alkyl" also embraces alkyl groups whose carbon chain may be interrupted by one or more nonadjacent groups selected from among -O-, -S-, -NR^e-, -CO- and/or -SO2- , where R^e is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. The expression "alkyl" also embraces substituted alkyl groups. Substituted alkyl groups can generally bear one or more than one (e.g. 1 , 2, 3, 4, 5 or more than 5) substituents. The substituents are preferably selected from among cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxy, mercapto, COOH, carboxylate, SO3H, sulfonate, NE¹E², nitro and cyano, wherein E¹ and E² are, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Carboxylate is a derivative of a carboxylic acid function, in particular a metal carboxylate, a carboxylic ester function or a carboxamide function. Sulfonate is a derivative of a sulfonic acid function, in particular a metal sulfonate, a sulfonic acid ester function or a sulfonamide function. Cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents of the alkyl group may be unsubstituted or substituted; suitable substituents are the substituents mentioned below for these groups.

The above statements regarding alkyl also apply to all alkyl moieties in alkoxy, alkylamino, alkylthio, alkylsulfinyl, alkylsulfonyl, etc.

Alkylene is a linear saturated hydrocarbon chain having from 1 to 10 and especially from 1 to 4 carbon atoms, such as ethane-1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl or hexane-1 ,6-diyl.

Aryl-substituted alkyl ("Arylalkyl") carries at least one unsubstituted or substituted aryl group as defined below. The alkyl moiety in "Arylalkyl" can carry at least one further substituent and/or its carbon chain may be interrupted by one or more nonadjacent groups selected from among -O-, -S-, -NR^e-, -CO- and/or -SO2-. Arylalkyl is preferably phenyl-Ci-Cio-alkyl, in particular phenyl-Ci-C4-alkyl, e.g. benzyl, 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1-yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl, 1-(phenmeth)-eth-1-yl, 1-(phenmethyl)-1-(methyl)-eth- 1-yl or 1-(phenmethyl)-1-(methyl)-prop-1-yl; preferably benzyl or 2-phenethyl.

For the purposes of the present invention, alkenyl embraces straight-chain and branched alkenyl groups which, depending on chain length, may carry one or more double bonds (e.g. 1 , 2, 3, 4 or more than 4). Preference is given to C2-C18 alkenyl groups, more preferably C2-C12 alkenyl groups. "Alkenyl" also embraces substituted alkenyl groups which can carry, for example, 1 , 2, 3, 4, 5 or more than 5 substituents. Examples of suitable substituents include cycloalkyl, heterocycloalkyl, aryl, heteroaryl, halogen, hydroxy, mercapto, COOH, carboxylate, SO3H, sulfonate, NE³E⁴, nitro and cyano, where E³ and E⁴ are, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Examples of alkenyl are ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, Penta-1 ,3-dien-1-yl, hexa-1 ,4-dien-1-yl, hexa-1 ,4-dien-3-yl, hexa-1 ,4-dien-6-yl, hexa-1 ,5-dien-1 -yl, hexa-1 ,5-dien-3-yl, hexa-1 ,5-dien-4-yl, hepta-1 ,4-dien-1-yl, hepta-1 ,4-dien-3-yl, hepta-1 ,4-dien-6-yl, hepta-1 ,4-dien-7-yl, hepta-1 ,5-dien-1-yl, hepta-1 ,5-dien-3-yl, hepta-1 ,5-dien-4-yl, hepta-1 ,5-dien-7-yl, hepta-1 ,6-dien-1-yl, hepta-1 ,6-dien-3-yl, hepta-1 ,6-dien-4-yl, hepta-1 ,6-dien-5-yl, hepta-1 ,6-dien-2-yl, octa-1 ,4-dien-1-yl, octa-1 ,4-dien-2-yl, octa-1 ,4-dien-3-yl, octa-1 ,4-dien-6-yl, octa-1 ,4-dien-7-yl, octa-1 ,5-dien-1 -yl, octa-1 ,5-dien-3-yl, octa-1 ,5-dien-4-yl, octa-1 ,5-dien-7-yl, octa-1 ,6-dien-1-yl, octa-1 ,6-dien-3-yl, octa-1 ,6-dien-4-yl, octa-1 ,6-dien-5-yl, octa-1 ,6-dien-2-yl, deca-1 ,4-dienyl, deca-1 ,5-dienyl, deca-1 ,6-dienyl, deca-1 ,7-dienyl, deca-1 ,8-dienyl, deca-2,5-dienyl, deca-2,6-dienyl, deca-2,7-dienyl, deca-2,8-dienyl, etc. The above remarks apply analogously to alkenyloxy, alkenylthio, etc.

For the purposes of the present invention, "alkynyl" embraces unsubstituted or substituted alkynyl groups which may carry one or more triple bonds. Preference is given to C2-C18 alkynyl groups, more preferably C2-C12 alkynyl groups. Examples of alkynyl are ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, and the like. The above remarks apply analogously to alkynyloxy, alkynylthio, etc. "Alkynyl" also embraces substituted alkynyl groups, which can carry, for example, 1 , 2, 3, 4, 5 or more than 5 radicals. Examples of suitable radicals for alkynyl are the same as those mentioned above as suitable radicals for "alkyl".

For the purposes of the present invention, the term "cycloalkyl" embraces both substituted and unsubstituted cycloalkyl groups, preferably Cs-Cs-cycloalkyl groups like cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, in particular Cs-Cs-cycloalkyl. Substituted cycloalkyl groups can carry, for example, 1 , 2, 3, 4, 5 or more than 5 substituents which are preferably selected independently of alkyl and substituents as defined above for "alkyl". Substituted cycloalkyl groups carry preferably one or more, e.g. 1 , 2, 3, 4 or 5, Ci-Cβ-alkyl groups.

Examples of preferred cycloalkyl groups are cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4-tert.-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and 4-tert.-butylcycloheptyl, cyclooctyl, 2-, 3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl, 3-, 4- and δ-propylcyclooctyl.

The term "cycloalkenyl" embraces unsubstituted and substituted monounsaturated hydrocarbon groups having 3 to 8, preferably 5 to 6, carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl and the like. Suitable substituents for cycloalkenyl are the same as those mentioned above for cycloalkyl.

For the purposes of the present invention, the term "aryl" embraces monocyclic or polycyclic aromatic hydrocarbon radicals which may be unsubstituted or unsubstituted. Aryl is preferably unsubstituted or substituted phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and in particular phenyl or naphthyl. Aryl, when substituted, may carry - depending on the number and size of the ring systems - one or more (e.g. 1 , 2, 3, 4, 5 or more than 5) substituents which are preferably selected independently of one another from among alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxy, mercapto, COOH, carboxylate, SO3H, sulfonate, NE⁵E⁶, nitro and cyano, where E⁵ und E⁶, independently of one another, are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Aryl is in particular phenyl which, when substituted, generally may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, substituents.

Aryl, which may be unsubstituted or substituted, is preferably 2-, 3- und 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisobutylphenyl,

2,4,6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl, 2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert.-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-tert.-butylphenyl and 2,4,6-tri-tert.-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl; 2-, 3- and 4-cyanophenyl. For the purposes of the present invention heterocycloalkyl embraces nonaromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms, in which 1 , 2 or 3 of the ring carbon atoms are replaced by heteroatoms selected from oxygen, nitrogen, sulfur, and a group -NR³-, said cycloaliphatic groups further being unsubstituted or substituted by one or more - for example, 1 , 2, 3, 4, 5 or 6 - Ci-Cβ alkyl groups. Examples that may be given of such heterocycloaliphatic groups include pyrrolidinyl, piperidinyl,

2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, dihydrothien-2-yl, tetrahydrofuranyl, dihydrofuran-2-yl, tetrahydropyranyl, 1 ,2-oxazolin- 5-yl, 1 ,3-oxazolin-2-yl, and dioxanyl.

For the purposes of the present invention heteroaryl embraces substituted or unsubstituted, heteroaromatic, monocyclic or polycyclic groups, preferably the groups pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1 ,2,3-triazolyl, 1 ,3,4-triazolyl, and carbazolyl, which, when substituted, can carry generally 1 , 2 or 3 substituents. The substituents are selected from d-Cε alkyl, d-Cε alkoxy, hydroxyl, carboxyl, halogen and cyano.

5- to 7-membered heterocycloalkyl or heteroaryl radicals bonded by a nitrogen atom and optionally containing further heteroatoms are, for example, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, piperidinyl, piperazinyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, indolyl, quinolinyl, isoquinolinyl or quinaldinyl.

For the purposes of the present invention, the term "polycyclic compounds" encompasses in the widest sense compounds which comprise at least two rings, regardless of how these rings are linked. The rings can be carbocyclic and/or heterocyclic. The rings can be linked via single or double bonds ("multinuclear compounds"), joined by fusion ("fused ring systems") or bridged ("bridged ring systems", "cage compounds"). Fused ring systems can be (fused-on) aromatic, hydroaromatic and cyclic compounds linked by fusion. Fused ring systems have two, three or more than three rings. Depending on the way in which the rings are linked, a distinction is made in the case of fused ring systems between ortho-fusion, i.e. each ring shares an edge or two atoms with each adjacent ring, and peri-fusion in which a carbon atom belongs to more than two rings. The bridged ring systems include, for the purposes of the present invention, those which do not belong to the multinuclear ring systems and fused ring systems and in which at least two ring atoms belong to at least two different rings. In the case of the bridged ring systems, a distinction is made, depending on the number of ring opening reactions formally required to obtain an open-chain compound, between bicyclo, tricyclo, tetracyclo compounds, etc., which comprise two, three, four, etc. rings. The bridged ring systems can, if desired, additionally have, depending on size, one, two, three or more than three fused-on rings.

The term "polycyclic compounds" comprises "bicycloalkyl". Bicycloalkyl preferably embraces bicyclic hydrocarbon groups having 5 to 10 carbon atoms, such as bicyclo[2.2.1]hept-1-yl, bicyclo[2.2.1]hept-2-yl, bicyclo[2.2.1]hept-7-yl, bicyclo[2.2.2]oct- 1-yl, bicyclo[2.2.2]oct-2-yl, bicyclo[3.3.0]octyl, bicyclo[4.4.0]decyl and the like.

As mentioned above, certain polycyclic aromatic hydrocarbon radicals which may be unsubstituted or unsubstituted are also referred to as "aryl" for the purposes of the present invention.

A preferred polycyclic aromatic group which comprises two rings is the 4,4'-biphenylen group.

For the purposes of the present invention, the term "polycyclic compounds" also encompasses porphyrins, phthalocyanins and further macrocyclic compounds.

The groups NE¹E², NE³E⁴, NE⁵E⁶ are preferably N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-diisopropylamino, N,N-di-n-butylamino, N,N-di-t-butylamino, N,N-dicyclohexylamino or N,N-diphenylamino.

Halogen is fluorine, chlorine, bromine or iodine.

Preferably, in the formulae Ia, Ib, Ic and Id, R^a and R^b are each independently selected from groups of the formulae 11.1 to 11.5:

(11-1 ) (II.2)

(II-3) (II.4)

# (A)_p — C(R^k)_y

(H-S)

where

# represents the bonding site to the imide nitrogen atom,

x in the groups of the formulae 11.1 to II.3 is 0, 1 , 2 or 3 and in the groups of the formula II.4 is 0, 1 or 2,

p is O or i ,

y is 2 or 3, where, in the case that y is 2, the carbon atom which bears the R^k radicals additionally bears a hydrogen atom,

A where present, is a Ci-Cio-alkylene group which may be interrupted by one or more nonadjacent groups which are selected from -O- and -S-,

the R¹ radicals are each independently selected from Ci-C3o-alkyl, Ci-C3o-alkyloxy, Ci-C3o-alkylthio, fluorine, chlorine, bromine, NE¹E², nitro and cyano, where E¹ and E², independently of one another, are hydrogen, Ci-C3o-alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,

the R^k radicals are each independently selected from C4-C3o-alkyl, C4-C3o-alkyloxy or

C4-C3o-alkylthio, wherein the alkyl groups may be interrupted by one or more nonadjacent oxygen atom(s).

Preferably, all residues R^a and R^b have the same meaning. Preferably, the R¹ radicals are each independently selected from Ci-Ci2-alkyl, C1-C12- alkyloxy and Ci-Ci2-alkylthio.

According to a preferred embodiment, the R¹ radicals are preferably selected from groups of the formula (I I. A)

(H-A)

in which the R^h radicals are selected from d-Cs-alkyl, preferably Ci-C3-alkyl.

In a special embodiment, the R¹ radicals are a group of the formula

Preferably, in the formulae Ia, Ib, Ic and Id, R^a and R^b are each independently selected from groups of the formula 11.1.

In a special embodiment all residues R^a and R^b are groups of the formula

According to a further preferred embodiment of the invention, in the compounds of the formulae Ia, Ib, Ic and Id, R^a and R^b are each independently selected from groups of the formula (II.5) (so-called swallowtail radicals). Preferably, all residues R^a and R^b that are selected from groups of the formula (II.5) have the same meaning.

In a preferred embodiment, the R^a and R^b groups that are selected from groups of the formula (II.5) do not comprise an alkylene group A. In a further preferred embodiment, the R^a and R^b groups that are selected from groups of the formula (11.5) comprise a Ci-C4-alkylene group A which may be interrupted by 1 , 2 or 3 nonadjacent groups selected from -O- and -S-. In the groups of the formula (11.5), the R^k radicals are preferably selected from C4-C12- alkyl, preferably Cs-Cs-alkyl. In that case, the R^a and R^b groups are preferably both a group of the formula

("-B) in which

# represents the bonding site to the imide nitrogen atom, and

the R¹ radicals are selected from C4-Ci2-alkyl, preferably Cs-Cs-alkyl.

In the groups of the formula (II. B), the R¹ radicals are especially linear alkyl radicals which are not interrupted by oxygen atoms.

Specific examples of suitable R^a and R^b groups include:

groups of the formula A

in which # is the bonding site to the imide nitrogen atom of the rylenetetracarboximide, p is an integer of 0, 1 , 2, 3, 4, 5 or 6, and R is C4-C3o-alkyl.

Examples of suitable radicals of the formula A comprise the formulae A-O. a, A-O. b, A-O.c, A-1.a, A-1.b, A-1.c, A-2.a, A-2.b, A-2.c, A-3.a, A-3.b, A-3.C, A-4.a, A-4.b, A-4.c, A-5.a, A-5.b, A-5.C, A-6.a, A-6.b, A-6.C

A-O.c

A-0.a A-O. b

A-2.C

A-2.a A-2.b

A-5.C

A-5.a A-5.b

A-6.C

A-6.a A-6.b

in which # is the bonding site to the imide nitrogen atom of the tetracarboximide group, and R is independently n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-docosanyl, n-tricosanyl, n-tetracosanyl, n-octacosanyl,

and additionally groups of the formula B

in which # is the bonding site to the imide nitrogen atom of the tetracarboximide group, p is an integer of 0, 1 , 2, 3, 4, 5 or 6, and R is C4-C3o-alkyl, C4-C3o-alkylthio or C4-C3o-alkoxy.

Radicals of the formula B comprise those in which p is 0, for example

1-ethylpropyl, 1-methylpropyl, 1-propylbutyl, 1-ethylbutyl, 1-methylbutyl, 1-butylpentyl, 1-propylpentyl, 1-ethylpentyl, 1-methylpentyl, 1-pentylhexyl, 1-butylhexyl, 1-propylhexyl, 1-ethylhexyl, 1-methylhexyl, 1-hexylheptyl, 1-pentylheptyl, 1-butylheptyl, 1-propylheptyl, 1-ethylheptyl, 1-methylheptyl, 1-heptyloctyl, 1-hexyloctyl, 1-pentyloctyl, 1-butyloctyl, 1-propyloctyl, 1-ethyloctyl, 1-methyloctyl, 1-octylnonyl, 1-heptylnonyl, 1-hexylnonyl, 1-pentylnonyl, 1-butylnonyl, 1-propylnonyl, 1-ethylnonyl, 1-methylnonyl, 1-nonyldecyl, 1-octyldecyl, 1-heptyldecyl, 1-hexyldecyl, 1-pentyldecyl, 1-butyldecyl, 1-propyldecyl, 1-ethyldecyl, 1-methyldecyl, 1-decylundecyl, 1-nonylundecyl,

1-octylundecyl, 1-heptylundecyl, 1-hexylundecyl, 1-pentylundecyl, 1-butylundecyl, 1-propylundecyl, 1-ethylundecyl, 1-methylundecyl, 1-undecyldodecyl, 1-decyldodecyl, 1-nonyldodecyl, 1-octyldodecyl, 1-heptyldodecyl, 1-hexyldodecyl, 1-pentyldodecyl, 1-butyldodecyl, 1-propyldodecyl, 1-ethyldodecyl, 1-methyldodecyl, 1-dodecyltridecyl, 1-undecyltridecyl, 1-decyltridecyl, 1-nonyltridecyl, 1-octyltridecyl, 1-heptyltridecyl, 1-hexyltridecyl, 1-pentyltridecyl, 1-butyltridecyl, 1-propyltridecyl, 1-ethyltridecyl, 1-methyltridecyl, 1-tridecyltetradecyl, 1-undecyltetradecyl, 1-decyltetradecyl, 1-nonyltetradecyl, 1-octyltetradecyl, 1-hetyltetradecyl, 1-hexyltetradecyl, 1-pentyltetradecyl, 1-butyltetradecyl, 1-propyltetradecyl, 1-ethyltetradecyl, 1-methyltetradecyl, 1-pentadecylhexadecyl, 1-tetradecylhexadecyl, 1-tridecylhexadecyl, 1-dodecylhexadecyl, 1-undecylhexadecyl, 1-decylhexadecyl, 1-nonylhexadecyl, 1-octylhexadecyl, 1-heptylhexadecyl, 1-hexylhexadecyl, 1-pentylhexadecyl, 1-butylhexadecyl, 1-propylhexadecyl, 1-ethylhexadecyl, 1-methylhexadecyl, 1 -hexadecyloctadecyl, 1 -pentadecyloctadecyl, 1 -tetrad ecyloctadecyl, 1-tridecyloctadecyl, 1-dodecyloctadecyl, 1-undecyloctadecyl, 1-decyloctadecyl, 1-nonyloctadecyl, 1-octyloctadecyl, 1-heptyloctadecyl, 1-hexyloctadecyl, 1-pentyloctadecyl, 1-butyloctadecyl, 1-propyloctadecyl, 1-ethyloctadecyl, 1-methyloctadecyl, 1-nonadecyleicosanyl, 1-octadecyleicosanyl, 1 -heptadecyleicosanyl, 1 -hexadecyleicosanyl, 1 -pentadecyleicosanyl, 1-tetradecyleicosanyl, 1-tridecyleicosanyl, 1-dodecyleicosanyl, 1-undecyleicosanyl, 1-decyleicosanyl, 1-nonyleicosanyl, 1-octyleicosanyl, 1-heptyleicosanyl, 1-hexyleicosanyl, 1-pentyleicosanyl, 1-butyleicosanyl, 1-propyleicosanyl, 1-ethyleicosanyl, 1-methyleicosanyl, 1-eicosanyldocosanyl, 1-nonadecyldocosanyl, 1 -octadecyldocosanyl, 1 -heptadecyldocosanyl, 1 -hexadecyldocosanyl, 1 -pentadecyldocosanyl, 1 -tetradecyldocosanyl, 1 -tridecyldocosanyl, 1-undecyldocosanyl, 1-decyldocosanyl, 1-nonyldocosanyl, 1-octyldocosanyl, 1-heptyldocosanyl, 1-hexyldocosanyl, 1-pentyldocosanyl, 1-butyldocosanyl, 1-propyldocosanyl, 1-ethyldocosanyl, 1-methyldocosanyl, 1-tricosanyltetracosanyl, 1-docosanyltetracosanyl, 1-nonadecyltetracosanyl, 1-octadecyltetracosanyl, 1 -heptadecyltetracosanyl, 1 -hexadecyltetracosanyl, 1 -pentadecyltetracosanyl, 1 -pentadecyltetracosanyl, 1 -tetradecyltetracosanyl, 1 -tridecyltetracosanyl, 1 -dodecyltetracosanyl, 1 -undecyltetracosanyl, 1 -decyltetracosanyl, 1-nonyltetracosanyl, 1-octyltetracosanyl, 1-heptyltetracosanyl, 1-hexyltetracosanyl, 1-pentyltetracosanyl, 1-butyltetracosanyl, 1-propyltetracosanyl, 1-ethyltetracosanyl, 1 -methyltetracosanyl, 1 -heptacosanyloctacosanyl, 1 -hexacosanyloctacosanyl, 1 -pentacosanyloctacosanyl, 1 -tetracosanyloctacosanyl, 1 -tricosanyloctacosanyl, 1 -docosanyloctacosanyl, 1 -nonadecyloctacosanyl, 1 -octadecyloctacosanyl, 1 -heptadecyloctacosanyl, 1 -hexadecyloctacosanyl, 1 -hexadecyloctacosanyl, 1-pentadecyloctacosanyl, 1-tetradecyloctacosanyl, 1-tridecyloctacosanyl,

1-dodecyloctacosanyl, 1-undecyloctacosanyl, 1-decyloctacosanyl, 1-nonyloctacosanyl, 1-octyloctacosanyl, 1-heptyloctacosanyl, 1-hexyloctacosanyl, 1-pentyloctacosanyl, 1-butyloctacosanyl, 1-propyloctacosanyl, 1-ethyloctacosanyl, 1-methyloctacosanyl;

1-ethyloxypropyl, 1-methyloxypropyl, 1-propylbutyl, 1-ethyloxybutyl, 1-methyloxybutyl, 1-butyloxypentyl, 1-propylpentyl, 1-ethyloxypentyl, 1-methyloxypentyl, 1-pentyloxyhexyl, 1-butyloxyhexyl, 1-propylhexyl, 1-ethyloxyhexyl, 1-methyloxyhexyl, 1-hexyloxyheptyl, 1-pentyloxyheptyl, 1-butyloxyheptyl, 1-propylheptyl, 1-ethyloxyheptyl, 1-methyloxyheptyl, 1-heptyloctyl, 1-hexyloxyoctyl, 1-pentyloxyoctyl, 1-butyloxyoctyl, 1-propyloctyl, 1-ethyloxyoctyl, 1-methyloxyoctyl, 1-octyloxynonyl, 1-heptylnonyl,

1-hexyloxynonyl, 1-pentyloxynonyl, 1-butyloxynonyl, 1-propylnonyl, 1-ethyloxynonyl, 1-methyloxynonyl, 1-nonyloxydecyl, 1-octyloxydecyl, 1-heptyldecyl, 1-hexyloxydecyl, 1-pentyloxydecyl, 1-butyloxydecyl, 1-propyldecyl, 1-ethyloxydecyl, 1-methyloxydecyl, 1-decyloxyundecyl, 1-nonyloxyundecyl, 1-octyloxyundecyl, 1-heptylundecyl, 1-hexyloxyundecyl, 1-pentyloxyundecyl, 1-butyloxyundecyl, 1 -propyl undecyl,

1-ethyloxyundecyl, 1-methyloxyundecyl, 1-undecyloxydodecyl, 1-decyloxydodecyl, 1-nonyloxydodecyl, 1-octyloxydodecyl, 1-heptyldodecyl, 1-hexyloxydodecyl, 1-pentyloxydodecyl, 1-butyloxydodecyl, 1-propyldodecyl, 1-ethyloxydodecyl, 1-methyloxydodecyl, 1-dodecyloxytridecyl, 1-undecyloxytridecyl, 1-decyloxytridecyl, 1-nonyloxytridecyl, 1-octyloxytridecyl, 1-heptyltridecyl, 1-hexyloxytridecyl, 1-pentyloxytridecyl, 1-butyloxytridecyl, 1-propyltridecyl, 1-ethyloxytridecyl, 1 -methyloxytridecyl, 1 -tridecyloxytetradecyl, 1 -undecyloxytetradecyl, 1-decyloxytetradecyl, 1-nonyloxytetradecyl, 1-octyloxytetradecyl, 1-hetyltetradecyl, 1-hexyloxytetradecyl, 1-pentyltetradecyl, 1-butyloxytetradecyl, 1-propyltetradecyl, 1 -ethyloxytetradecyl, 1 -methyloxytetradecyl, 1 -pentadecyloxyhexadecyl, 1 -tetradecyloxyhexadecyl, 1 -tridecyloxyhexadecyl, 1 -dodecyloxyhexadecyl, 1 -undecyloxyhexadecyl, 1 -decyloxyhexadecyl, 1 -nonyloxyhexadecyl, 1-octyloxyhexadecyl, 1-heptylhexadecyl, 1-hexyloxyhexadecyl, 1-pentyloxyhexadecyl, 1-butyloxyhexadecyl, 1-propylhexadecyl, 1-ethyloxyhexadecyl, 1-methyloxyhexadecyl, 1 -hexadecyloxyoctadecyl, 1 -pentadecyloxyoctadecyl, 1 -tetrad ecyloxyoctadecyl, 1 -tridecyloxyoctadecyl, 1 -dodecyloxyoctadecyl, 1 -und ecyloxyoctadecyl, 1-d ecyloxyoctadecyl, 1-nonyloxyoctadecyl, 1-octyloxyoctadecyl, 1-heptyloctadecyl, 1-hexyloxyoctadecyl, 1-pentyloxyoctadecyl, 1-butyloxyoctadecyl, 1-propyloctadecyl, 1-ethyloxyoctadecyl, 1-methyloxyoctadecyl, 1-nonadecyloxyeicosanyl,

1 -octadecyloxyeicosanyl, 1 -heptadecyloxyeicosanyl, 1 -hexadecyloxyeicosanyl, 1 -pentadecyloxyeicosanyl, 1 -tetradecyloxyeicosanyl, 1 -tridecyloxyeicosanyl, 1 -dodecyloxyeicosanyl, 1 -undecyloxyeicosanyl, 1 -decyloxyeicosanyl, 1-nonyloxyeicosanyl, 1-octyloxyeicosanyl, 1-heptyleicosanyl, 1-hexyloxyeicosanyl, 1-pentyloxyeicosanyl, 1-butyloxyeicosanyl, 1-propyleicosanyl, 1-ethyloxyeicosanyl, 1 -methyleicosanyl, 1 -eicosanyloxydocosanyl, 1 -nonadecyloxydocosanyl, 1 -octadecyloxydocosanyl, 1 -heptadecyloxydocosanyl, 1 -hexadecyloxydocosanyl, 1 -pentadecyloxydocosanyl, 1 -tetradecyloxydocosanyl, 1 -tridecyloxydocosanyl, 1 -undecyloxydocosanyl, 1 -decyloxydocosanyl, 1 -nonyloxydocosanyl, 1-octyloxydocosanyl, 1-heptyldocosanyl, 1-hexyloxydocosanyl, 1-pentyloxydocosanyl, 1-butyloxydocosanyl, 1-propyldocosanyl, 1-ethyloxydocosanyl, 1-methyloxydocosanyl, 1 -tricosanyloxytetracosanyl, 1 -docosanyloxytetracosanyl, 1 -nonadecyloxytetracosanyl, 1 -octadecyloxytetracosanyl, 1 -heptadecyloxytetracosanyl, 1 -hexadecyloxytetracosanyl, 1 -pentadecyloxytetracosanyl, 1 -pentadecyloxytetracosanyl, 1-tetradecyloxytetracosanyl, 1-tridecyloxytetracosanyl, 1-dodecyloxytetracosanyl, 1 -undecyloxytetracosanyl, 1 -decyloxytetracosanyl, 1 -nonyloxytetracosanyl, 1 -octyloxytetracosanyl, 1 -heptyltetracosanyl, 1 -hexyloxytetracosanyl, 1-pentyloxytetracosanyl, 1-butyloxytetracosanyl, 1-propyltetracosanyl, 1 -ethyloxytetracosanyl, 1 -methyloxytetracosanyl, 1 -heptacosanyloxyoctacosanyl, 1-hexacosanyloxyoctacosanyl, 1-pentacosanyloxyoctacosanyl, 1 -tetracosanyloxyoctacosanyl, 1 -tricosanyloxyoctacosanyl,

1 -docosanyloxyoctacosanyl, 1 -nonadecyloxyoctacosanyl, 1 -octadecyloxyoctacosanyl, 1 -heptadecyloxyoctacosanyl, 1 -hexadecyloxyoctacosanyl, 1 -hexadecyloxyoctacosanyl, 1 -pentadecyloxyoctacosanyl, 1 -tetradecyloxyoctacosanyl, 1 -tridecyloxyoctacosanyl, 1-dodecyloxyoctacosanyl, 1-undecyloxyoctacosanyl, 1-decyloxyoctacosanyl, 1 -nonyloxyoctacosanyl, 1 -octyloxyoctacosanyl, 1 -heptyloctacosanyl, 1-hexyloxyoctacosanyl, 1-pentyloxyoctacosanyl, 1-butyloxyoctacosanyl, 1 -propyloxyoctacosanyl, 1 -ethyloxyoctacosanyl, 1 -methyloxyoctacosanyl; 1-ethylthiopropyl, 1-methylthiopropyl, 1-propylbutyl, 1-ethylthiobutyl, 1-methylthiobutyl, 1-butylthiopentyl, 1-propylpentyl, 1-ethylthiopentyl, 1-methylthiopentyl, 1-pentylthiohexyl, 1-butylthiohexyl, 1-propylhexyl, 1-ethylthiohexyl, 1-methylthiohexyl, 1-hexylthioheptyl, 1-pentylthioheptyl, 1-butylthioheptyl, 1-propylheptyl, 1-ethylthioheptyl, 1-methylthioheptyl, 1-heptyloctyl, 1-hexylthiooctyl, 1-pentylthiooctyl, 1-butylthiooctyl, 1-propyloctyl, 1-ethylthiooctyl, 1-methylthiooctyl, 1-octylthiononyl, 1-heptylnonyl, 1-hexylthiononyl, 1-pentylthiononyl, 1-butylthiononyl, 1-propylnonyl, 1-ethylthiononyl, 1-methylthiononyl, 1-nonylthiodecyl, 1-octylthiodecyl, 1-heptyldecyl, 1-hexylthiodecyl, 1-pentylthiodecyl, 1-butylthiodecyl, 1-propyldecyl, 1-ethylthiodecyl, 1-methylthiodecyl, 1-decylthioundecyl, 1-nonylthioundecyl, 1-octylthioundecyl, 1-heptylundecyl, 1-hexylthioundecyl, 1-pentylthioundecyl, 1-butylthioundecyl, 1-propylundecyl, 1-ethylthioundecyl, 1-methylthioundecyl, 1-undecylthiododecyl, 1-decylthiododecyl, 1-nonylthiododecyl, 1-octylthiododecyl, 1-heptyldodecyl, 1-hexylthiododecyl, 1-pentylthiododecyl, 1-butylthiododecyl, 1-propyldodecyl, 1-ethylthiododecyl, 1-methylthiododecyl, 1-dodecylthiotridecyl, 1-undecylthiotridecyl, 1-decylthiotridecyl, 1-nonylthiotridecyl, 1 -octylthiotridecyl, 1 -heptyltridecyl, 1 -hexylthiotridecyl, 1-pentylthiotridecyl, 1 -butylthiotridecyl, 1-propyltridecyl, 1-ethylthiotridecyl, 1-methylthiotridecyl, 1-tridecylthiotetradecyl, 1-undecylthiotetradecyl, 1-decylthiotetradecyl, 1-nonylthiotetradecyl, 1-octylthiotetradecyl, 1-hetyltetradecyl, 1-hexylthiotetradecyl, 1-pentyltetradecyl, 1-butylthiotetradecyl, 1-propyltetradecyl, 1 -ethylthiotetradecyl, 1 -methylthiotetradecyl, 1 -pentadecylthiohexadecyl, 1 -tetradecylthiohexadecyl, 1 -tridecylthiohexadecyl, 1 -dodecylthiohexadecyl, 1 -undecylthiohexadecyl, 1 -decylthiohexadecyl, 1 -nonylthiohexadecyl, 1-octylthiohexadecyl, 1-heptylhexadecyl, 1-hexylthiohexadecyl, 1-pentylthiohexadecyl, 1-butylthiohexadecyl, 1-propylhexadecyl, 1-ethylthiohexadecyl, 1-methylthiohexadecyl, 1 -hexadecylthiooctadecyl, 1 -pentadecylthiooctadecyl, 1 -tetradecylthiooctadecyl, 1 -tridecylthiooctadecyl, 1 -dodecylthiooctadecyl, 1 -undecylthiooctadecyl, 1-decylthiooctadecyl, 1-nonylthiooctadecyl, 1-octylthiooctadecyl, 1-heptyloctadecyl, 1-hexylthiooctadecyl, 1-pentylthiooctadecyl, 1-butylthiooctadecyl, 1-propyloctadecyl, 1-ethylthiooctadecyl, 1-methylthiooctadecyl, 1-nonadecylthioeicosanyl,

1 -octadecylthioeicosanyl, 1 -heptadecylthioeicosanyl, 1 -hexadecylthioeicosanyl, 1 -pentadecylthioeicosanyl, 1 -tetradecylthioeicosanyl, 1 -tridecylthioeicosanyl, 1 -dodecylthioeicosanyl, 1 -undecylthioeicosanyl, 1 -decylthioeicosanyl, 1-nonylthioeicosanyl, 1-octylthioeicosanyl, 1-heptyleicosanyl, 1-hexylthioeicosanyl, 1-pentylthioeicosanyl, 1-butylthioeicosanyl, 1-propyleicosanyl, 1-ethylthioeicosanyl, 1 -methyleicosanyl, 1 -eicosanylthiodocosanyl, 1 -nonadecylthiodocosanyl, 1 -octadecylthiodocosanyl, 1 -heptadecylthiodocosanyl, 1 -hexadecylthiodocosanyl, 1 -pentadecylthiodocosanyl, 1 -tetradecylthiodocosanyl, 1 -tridecylthiodocosanyl, 1 -undecylthiodocosanyl, 1 -decylthiodocosanyl, 1 -nonylthiodocosanyl, 1-octylthiodocosanyl, 1-heptyldocosanyl, 1-hexylthiodocosanyl, 1-pentylthiodocosanyl, 1-butylthiodocosanyl, 1-propyldocosanyl, 1-ethylthiodocosanyl, 1-methylthiodocosanyl, 1 -tricosanylthiotetracosanyl, 1 -docosanylthiotetracosanyl, 1 -nonadecylthiotetracosanyl, 1 -octadecylthiotetracosanyl, 1 -heptadecylthiotetracosanyl, 1 -hexadecylthiotetracosanyl, 1-pentadecylthiotetracosanyl, 1-pentadecylthiotetracosanyl,

1 -tetradecylthiotetracosanyl, 1 -tridecylthiotetracosanyl, 1 -dodecylthiotetracosanyl, 1 -undecylthiotetracosanyl, 1 -decylthiotetracosanyl, 1 -nonylthiotetracosanyl, 1 -octylthiotetracosanyl, 1 -heptyltetracosanyl, 1 -hexylthiotetracosanyl, 1-pentylthiotetracosanyl, 1-butylthiotetracosanyl, 1-propyltetracosanyl, 1-ethylthiotetracosanyl, 1-methylthiotetracosanyl, i-heptacosanylthiooctacosanyl, 1 -hexacosanylthiooctacosanyl, 1 -pentacosanylthiooctacosanyl, 1 -tetracosanylthiooctacosanyl, 1 -tricosanylthiooctacosanyl,

1 -docosanylthiooctacosanyl, 1 -nonadecylthiooctacosanyl, 1 -octadecylthiooctacosanyl, 1 -heptadecylthiooctacosanyl, 1 -hexadecylthiooctacosanyl, 1 -hexadecylthiooctacosanyl, i-pentadecylthiooctacosanyl, i-tetradecylthiooctacosanyl, i-tridecylthiooctacosanyl, 1 -dodecylthiooctacosanyl, 1 -undecylthiooctacosanyl, 1 -decylthiooctacosanyl, 1 -nonylthiooctacosanyl, 1 -octylthiooctacosanyl, 1 -heptyloctacosanyl, 1-hexylthiooctacosanyl, 1-pentylthiooctacosanyl, 1-butylthiooctacosanyl, 1-propylthiooctacosanyl, 1-ethylthiooctacosanyl, 1-methylthiooctacosanyl;

in which p is 1 , for example

2-ethylpropyl, 2-methylpropyl, 2-propylbutyl, 2-ethylbutyl, 2-methylbutyl, 2-butylpentyl, 2-propylpentyl, 2-ethylpentyl, 2-methylpentyl, 2-pentylhexyl, 2-butylhexyl, 2-propylhexyl, 2-ethylhexyl, 2-methylhexyl, 2-hexylheptyl, 2-pentylheptyl, 2-butylheptyl, 2-propylheptyl, 2-ethylheptyl, 2-methylheptyl, 2-heptyloctyl, 2-hexyloctyl, 2-pentyloctyl, 2-butyloctyl, 2-propyloctyl, 2-ethyloctyl, 2-methyloctyl, 2-octylnonyl, 2-heptylnonyl, 2-hexylnonyl, 2-pentylnonyl, 2-butylnonyl, 2-propylnonyl, 2-ethylnonyl, 2-methylnonyl, 2-nonyldecyl, 2-octyldecyl, 2-heptyldecyl, 2-hexyldecyl, 2-pentyldecyl, 2-butyldecyl, 2-propyldecyl, 2-ethyldecyl, 2-methyldecyl, 2-decylundecyl, 2-nonylundecyl,

2-octylundecyl, 2-heptylundecyl, 2-hexylundecyl, 2-pentylundecyl, 2-butylundecyl, 2-propylundecyl, 2-ethylundecyl, 2-methylundecyl, 2-undecyldodecyl, 2-decyldodecyl, 2-nonyldodecyl, 2-octyldodecyl, 2-heptyldodecyl, 2-hexyldodecyl, 2-pentyldodecyl, 2-butyldodecyl, 2-propyldodecyl, 2-ethyldodecyl, 2-methyldodecyl, 2-dodecyltridecyl, 2-undecyltridecyl, 2-decyltridecyl, 2-nonyltridecyl, 2-octyltridecyl, 2-heptyltridecyl, 2-hexyltridecyl, 2-pentyltridecyl, 2-butyltridecyl, 2-propyltridecyl, 2-ethyltridecyl, 2-methyltridecyl, 2-tridecyltetradecyl, 2-undecyltetradecyl, 2-decyltetradecyl, 2-nonyltetradecyl, 2-octyltetradecyl, 2-hetyltetradecyl, 2-hexyltetradecyl, 2-pentyltetradecyl, 2-butyltetradecyl, 2-propyltetradecyl, 2-ethyltetradecyl, 2-methyltetradecyl, 2-pentadecylhexadecyl, 2-tetradecylhexadecyl, 2-tridecylhexadecyl, 2-dodecylhexadecyl, 2-undecylhexadecyl, 2-decylhexadecyl, 2-nonylhexadecyl, 2-octylhexadecyl, 2-heptylhexadecyl, 2-hexylhexadecyl, 2-pentylhexadecyl, 2-butylhexadecyl, 2-propylhexadecyl, 2-ethylhexadecyl, 2-methylhexadecyl, 2-hexadecyloctadecyl, 2-pentadecyloctadecyl,

2-tetradecyloctadecyl, 2-tridecyloctadecyl, 2-dodecyloctadecyl, 2-undecyloctadecyl, 2-decyloctadecyl, 2-nonyloctadecyl, 2-octyloctadecyl, 2-heptyloctadecyl, 2-hexyloctadecyl, 2-pentyloctadecyl, 2-butyloctadecyl, 2-propyloctadecyl, 2-ethyloctadecyl, 2-methyloctadecyl, 2-nonadecyleicosanyl, 2-octadecyleicosanyl, 2-heptadecyleicosanyl, 2-hexadecyleicosanyl, 2-pentadecyleicosanyl,

2-tetradecyleicosanyl, 2-tridecyleicosanyl, 2-dodecyleicosanyl, 2-undecyleicosanyl, 2-decyleicosanyl, 2-nonyleicosanyl, 2-octyleicosanyl, 2-heptyleicosanyl, 2-hexyleicosanyl, 2-pentyleicosanyl, 2-butyleicosanyl, 2-propyleicosanyl, 2-ethyleicosanyl, 2-methyleicosanyl, 2-eicosanyldocosanyl, 2-nonadecyldocosanyl, 2-octadecyldocosanyl, 2-heptadecyldocosanyl, 2-hexadecyldocosanyl, 2-pentadecyldocosanyl, 2-tetradecyldocosanyl, 2-tridecyldocosanyl, 2-undecyldocosanyl, 2-decyldocosanyl, 2-nonyldocosanyl, 2-octyldocosanyl, 2-heptyldocosanyl, 2-hexyldocosanyl, 2-pentyldocosanyl, 2-butyldocosanyl, 2-propyldocosanyl, 2-ethyldocosanyl, 2-methyldocosanyl, 2-tricosanyltetracosanyl, 2-docosanyltetracosanyl, 2-nonadecyltetracosanyl, 2-octadecyltetracosanyl, 2-heptadecyltetracosanyl, 2-hexadecyltetracosanyl, 2-pentadecyltetracosanyl, 2-pentadecyltetracosanyl, 2-tetradecyltetracosanyl, 2-tridecyltetracosanyl, 2-dodecyltetracosanyl, 2-undecyltetracosanyl, 2-decyltetracosanyl, 2-nonyltetracosanyl, 2-octyltetracosanyl, 2-heptyltetracosanyl, 2-hexyltetracosanyl, 2-pentyltetracosanyl, 2-butyltetracosanyl, 2-propyltetracosanyl, 2-ethyltetracosanyl, 2-methyltetracosanyl, 2-heptacosanyloctacosanyl, 2-hexacosanyloctacosanyl, 2-pentacosanyloctacosanyl, 2-tetracosanyloctacosanyl, 2-tricosanyloctacosanyl, 2-docosanyloctacosanyl, 2-nonadecyloctacosanyl, 2-octadecyloctacosanyl, 2-heptadecyloctacosanyl, 2-hexadecyloctacosanyl, 2-hexadecyloctacosanyl, 2-pentadecyloctacosanyl, 2-tetradecyloctacosanyl, 2-tridecyloctacosanyl,

2-dodecyloctacosanyl, 2-undecyloctacosanyl, 2-decyloctacosanyl, 2-nonyloctacosanyl, 2-octyloctacosanyl, 2-heptyloctacosanyl, 2-hexyloctacosanyl, 2-pentyloctacosanyl, 2-butyloctacosanyl, 2-propyloctacosanyl, 2-ethyloctacosanyl, 2-methyloctacosanyl;

in which p is 2, such as

3-ethylpropyl, 3-methylpropyl, 3-propylbutyl, 3-ethylbutyl, 3-methylbutyl, 3-butylpentyl, 3-propylpentyl, 3-ethylpentyl, 3-methylpentyl, 3-pentylhexyl, 3-butylhexyl, 3-propylhexyl, 3-ethylhexyl, 3-methylhexyl, 3-hexylheptyl, 3-pentylheptyl, 3-butylheptyl, 3-propylheptyl, 3-ethylheptyl, 3-methylheptyl, 3-heptyloctyl, 3-hexyloctyl, 3-pentyloctyl, 3-butyloctyl, 3-propyloctyl, 3-ethyloctyl, 3-methyloctyl, 3-octylnonyl, 3-heptylnonyl, 3-hexylnonyl, 3-pentylnonyl, 3-butylnonyl, 3-propylnonyl, 3-ethylnonyl, 3-methylnonyl, 3-nonyldecyl, 3-octyldecyl, 3-heptyldecyl, 3-hexyldecyl, 3-pentyldecyl, 3-butyldecyl, 3-propyldecyl, 3-ethyldecyl, 3-methyldecyl, 3-decylundecyl, 3-nonylundecyl,

3-octylundecyl, 3-heptylundecyl, 3-hexylundecyl, 3-pentylundecyl, 3-butylundecyl, 3-propylundecyl, 3-ethylundecyl, 3-methylundecyl, 3-undecyldodecyl, 3-decyldodecyl, 3-nonyldodecyl, 3-octyldodecyl, 3-heptyldodecyl, 3-hexyldodecyl, 3-pentyldodecyl, 3-butyldodecyl, 3-propyldodecyl, 3-ethyldodecyl, 3-methyldodecyl, 3-dodecyltridecyl, 3-undecyltridecyl, 3-decyltridecyl, 3-nonyltridecyl, 3-octyltridecyl, 3-heptyltridecyl, 3-hexyltridecyl, 3-pentyltridecyl, 3-butyltridecyl, 3-propyltridecyl, 3-ethyltridecyl, 3-methyltridecyl, 3-tridecyltetradecyl, 3-undecyltetradecyl, 3-decyltetradecyl, 3-nonyltetradecyl, 3-octyltetradecyl, 3-hetyltetradecyl, 3-hexyltetradecyl, 3-pentyltetradecyl, 3-butyltetradecyl, 3-propyltetradecyl, 3-ethyltetradecyl, 3-methyltetradecyl, 3-pentadecylhexadecyl, 3-tetradecylhexadecyl, 3-tridecylhexadecyl, 3-dodecylhexadecyl, 3-undecylhexadecyl, 3-decylhexadecyl, 3-nonylhexadecyl, 3-octylhexadecyl, 3-heptylhexadecyl, 3-hexylhexadecyl, 3-pentylhexadecyl, 3-butylhexadecyl, 3-propylhexadecyl, 3-ethylhexadecyl, 3-methylhexadecyl, 3-hexadecyloctadecyl, 3-pentadecyloctadecyl, 3-tetradecyloctadecyl, 3-tridecyloctadecyl, 3-dodecyloctadecyl, 3-undecyloctadecyl, 3-decyloctadecyl, 3-nonyloctadecyl, 3-octyloctadecyl, 3-heptyloctadecyl, 3-hexyloctadecyl, 3-pentyloctadecyl, 3-butyloctadecyl, 3-propyloctadecyl, 3-ethyloctadecyl, 3-methyloctadecyl, 3-nonadecyleicosanyl, 3-octadecyleicosanyl, 3-heptadecyleicosanyl, 3-hexadecyleicosanyl, 3-pentadecyleicosanyl, 3-tetradecyleicosanyl, 3-tridecyleicosanyl, 3-dodecyleicosanyl, 3-undecyleicosanyl, 3-decyleicosanyl, 3-nonyleicosanyl, 3-octyleicosanyl, 3-heptyleicosanyl, 3-hexyleicosanyl, 3-pentyleicosanyl, 3-butyleicosanyl, 3-propyleicosanyl, 3-ethyleicosanyl, 3-methyleicosanyl, 3-eicosanyldocosanyl, 3-nonadecyldocosanyl, 3-octadecyldocosanyl, 3-heptadecyldocosanyl, 3-hexadecyldocosanyl, 3-pentadecyldocosanyl, 3-tetradecyldocosanyl, 3-tridecyldocosanyl,

3-undecyldocosanyl, 3-decyldocosanyl, 3-nonyldocosanyl, 3-octyldocosanyl, 3-heptyldocosanyl, 3-hexyldocosanyl, 3-pentyldocosanyl, 3-butyldocosanyl, 3-propyldocosanyl, 3-ethyldocosanyl, 3-methyldocosanyl, 3-tricosanyltetracosanyl, 3-docosanyltetracosanyl, 3-nonadecyltetracosanyl, 3-octadecyltetracosanyl, 3-heptadecyltetracosanyl, 3-hexadecyltetracosanyl, 3-pentadecyltetracosanyl, 3-pentadecyltetracosanyl, 3-tetradecyltetracosanyl, 3-tridecyltetracosanyl, 3-dodecyltetracosanyl, 3-undecyltetracosanyl, 3-decyltetracosanyl, 3-nonyltetracosanyl, 3-octyltetracosanyl, 3-heptyltetracosanyl, 3-hexyltetracosanyl, 3-pentyltetracosanyl, 3-butyltetracosanyl, 3-propyltetracosanyl, 3-ethyltetracosanyl, 3-methyltetracosanyl, S-heptacosanyloctacosanyl, 3-hexacosanyloctacosanyl, S-pentacosanyloctacosanyl, 3-tetracosanyloctacosanyl, 3-tricosanyloctacosanyl, 3-docosanyloctacosanyl, 3-nonadecyloctacosanyl, 3-octadecyloctacosanyl, 3-heptadecyloctacosanyl, 3-hexadecyloctacosanyl, 3-hexadecyloctacosanyl, 3-pentadecyloctacosanyl, 3-tetradecyloctacosanyl, 3-tridecyloctacosanyl,

3-dodecyloctacosanyl, 3-undecyloctacosanyl, 3-decyloctacosanyl, 3-nonyloctacosanyl, 3-octyloctacosanyl, 3-heptyloctacosanyl, 3-hexyloctacosanyl, 3-pentyloctacosanyl, 3-butyloctacosanyl, 3-propyloctacosanyl, 3-ethyloctacosanyl, 3-methyloctacosanyl,

in which p is 3, such as

4-butylpentyl, 4-propylpentyl, 4-ethylpentyl, 4-methylpentyl, 4-pentylhexyl, 4-butylhexyl, 4-propylhexyl, 4-ethylhexyl, 4-methylhexyl, 4-hexylheptyl, 4-pentylheptyl, 4-butylheptyl, 4-propylheptyl, 4-ethylheptyl, 4-methylheptyl, 4-heptyloctyl, 4-hexyloctyl, 4-pentyloctyl, 4-butyloctyl, 4-propyloctyl, 4-ethyloctyl, 4-methyloctyl, 4-octylnonyl, 4-heptylnonyl,

4-hexylnonyl, 4-pentylnonyl, 4-butylnonyl, 4-propylnonyl, 4-ethylnonyl, 4-methylnonyl, 4-nonyldecyl, 4-octyldecyl, 4-heptyldecyl, 4-hexyldecyl, 4-pentyldecyl, 4-butyldecyl, 4-propyldecyl, 4-ethyldecyl, 4-methyldecyl, 4-decylundecyl, 4-nonylundecyl, 4-octylundecyl, 4-heptylundecyl, 4-hexylundecyl, 4-pentylundecyl, 4-butylundecyl, 4-propylundecyl, 4-ethylundecyl, 4-methylundecyl, 4-undecyldodecyl, 4-decyldodecyl, 4-nonyldodecyl, 4-octyldodecyl, 4-heptyldodecyl, 4-hexyldodecyl, 4-pentyldodecyl, 4-butyldodecyl, 4-propyldodecyl, 4-ethyldodecyl, 4-methyldodecyl, 4-dodecyltridecyl, 4-undecyltridecyl, 4-decyltridecyl, 4-nonyltridecyl, 4-octyltridecyl, 4-heptyltridecyl, 4-hexyltridecyl, 4-pentyltridecyl, 4-butyltridecyl, 4-propyltridecyl, 4-ethyltridecyl, 4-methyltridecyl, 4-tridecyltetradecyl, 4-undecyltetradecyl, 4-decyltetradecyl, 4-nonyltetradecyl, 4-octyltetradecyl, 4-hetyltetradecyl, 4-hexyltetradecyl, 4-pentyltetradecyl, 4-butyltetradecyl, 4-propyltetradecyl, 4-ethyltetradecyl, 4-methyltetradecyl, 4-pentadecylhexadecyl, 4-tetradecylhexadecyl, 4-tridecylhexadecyl, 4-dodecylhexadecyl, 4-undecylhexadecyl, 4-decylhexadecyl, 4-nonylhexadecyl, 4-octylhexadecyl, 4-heptylhexadecyl, 4-hexylhexadecyl, 4-pentylhexadecyl, 4-butylhexadecyl, 4-propylhexadecyl, 4-ethylhexadecyl, 4-methylhexadecyl, 4-hexadecyloctadecyl, 4-pentadecyloctadecyl, 4-tetradecyloctadecyl, 4-tridecyloctadecyl, 4-dodecyloctadecyl, 4-undecyloctadecyl, 4-decyloctadecyl, 4-nonyloctadecyl, 4-octyloctadecyl, 4-heptyloctadecyl, 4-hexyloctadecyl, 4-pentyloctadecyl, 4-butyloctadecyl, 4-propyloctadecyl, 4-ethyloctadecyl, 4-methyloctadecyl, 4-nonadecyleicosanyl, 4-octadecyleicosanyl, 4-heptadecyleicosanyl, 4-hexadecyleicosanyl, 4-pentadecyleicosanyl, 4-tetradecyleicosanyl, 4-tridecyleicosanyl, 4-dodecyleicosanyl, 4-undecyleicosanyl, 4-decyleicosanyl, 4-nonyleicosanyl, 4-octyleicosanyl, 4-heptyleicosanyl, 4-hexyleicosanyl, 4-pentyleicosanyl, 4-butyleicosanyl, 4-propyleicosanyl, 4-ethyleicosanyl, 4-methyleicosanyl, 4-eicosanyldocosanyl, 4-nonadecyldocosanyl, 4-octadecyldocosanyl, 4-heptadecyldocosanyl, 4-hexadecyldocosanyl, 4-pentadecyldocosanyl, 4-tetradecyldocosanyl, 4-tridecyldocosanyl, 4-undecyldocosanyl, 4-decyldocosanyl, 4-nonyldocosanyl, 4-octyldocosanyl, 4-heptyldocosanyl, 4-hexyldocosanyl, 4-pentyldocosanyl, 4-butyldocosanyl, 4-propyldocosanyl, 4-ethyldocosanyl, 4-methyldocosanyl, 4-tricosanyltetracosanyl, 4-docosanyltetracosanyl, 4-nonadecyltetracosanyl, 4-octadecyltetracosanyl, 4-heptadecyltetracosanyl, 4-hexadecyltetracosanyl, 4-pentadecyltetracosanyl, 4-pentadecyltetracosanyl, 4-tetradecyltetracosanyl, 4-tridecyltetracosanyl, 4-dodecyltetracosanyl, 4-undecyltetracosanyl, 4-decyltetracosanyl, 4-nonyltetracosanyl, 4-octyltetracosanyl, 4-heptyltetracosanyl, 4-hexyltetracosanyl, 4-pentyltetracosanyl, 4-butyltetracosanyl, 4-propyltetracosanyl, 4-ethyltetracosanyl, 4-methyltetracosanyl, 4-heptacosanyloctacosanyl, 4-hexacosanyloctacosanyl, 4-pentacosanyloctacosanyl, 4-tetracosanyloctacosanyl, 4-tricosanyloctacosanyl, 4-docosanyloctacosanyl, 4-nonadecyloctacosanyl, 4-octadecyloctacosanyl, 4-heptadecyloctacosanyl, 4-hexadecyloctacosanyl, 4-hexadecyloctacosanyl, 4-pentadecyloctacosanyl, 4-tetradecyloctacosanyl, 4-tridecyloctacosanyl, 4-dodecyloctacosanyl, 4-undecyloctacosanyl, 4-decyloctacosanyl, 4-nonyloctacosanyl, 4-octyloctacosanyl, 4-heptyloctacosanyl, 4-hexyloctacosanyl, 4-pentyloctacosanyl, 4-butyloctacosanyl, 4-propyloctacosanyl, 4-ethyloctacosanyl, 4-methyloctacosanyl,

in which p is 4, such as

5-pentylhexyl, 5-butylhexyl, 5-propylhexyl, 5-ethylhexyl, 5-methylhexyl, 5-hexylheptyl, 5-pentylheptyl, 5-butylheptyl, 5-propylheptyl, 5-ethylheptyl, 5-methylheptyl, 5-heptyloctyl, 5-hexyloctyl, 5-pentyloctyl, 5-butyloctyl, 5-propyloctyl, 5-ethyloctyl, 5-methyloctyl, 5-octylnonyl, 5-heptylnonyl, 5-hexylnonyl, 5-pentylnonyl, 5-butylnonyl, 5-propylnonyl, 5-ethylnonyl, 5-methylnonyl, 5-nonyldecyl, 5-octyldecyl, 5-heptyldecyl, 5-hexyldecyl, 5-pentyldecyl, 5-butyldecyl, 5-propyldecyl, 5-ethyldecyl, 5-methyldecyl, 5-decylundecyl, 5-nonylundecyl, 5-octylundecyl, 5-heptylundecyl, 5-hexylundecyl, 5-pentylundecyl, 5-butylundecyl, 5-propylundecyl, 5-ethylundecyl, 5-methylundecyl, 5-undecyldodecyl, 5-decyldodecyl, 5-nonyldodecyl, 5-octyldodecyl, 5-heptyldodecyl, 5-hexyldodecyl, 5-pentyldodecyl, 5-butyldodecyl, 5-propyldodecyl, 5-ethyldodecyl, 5-methyldodecyl, 5-dodecyltridecyl, 5-undecyltridecyl, 5-decyltridecyl, 5-nonyltridecyl, 5-octyltridecyl, 5-heptyltridecyl, 5-hexyltridecyl, 5-pentyltridecyl, 5-butyltridecyl, 5-propyltridecyl, 5-ethyltridecyl, 5-methyltridecyl, 5-tridecyltetradecyl, 5-undecyltetradecyl, 5-decyltetradecyl, 5-nonyltetradecyl, 5-octyltetradecyl, 5-hetyltetradecyl, 5-hexyltetradecyl, 5-pentyltetradecyl, 5-butyltetradecyl, 5-propyltetradecyl, 5-ethyltetradecyl, 5-methyltetradecyl, 5-pentadecylhexadecyl, 5-tetradecylhexadecyl, 5-tridecylhexadecyl, 5-dodecylhexadecyl, 5-undecylhexadecyl, 5-decylhexadecyl, 5-nonylhexadecyl, 5-octylhexadecyl, 5-heptylhexadecyl, 5-hexylhexadecyl, 5-pentylhexadecyl, 5-butylhexadecyl, 5-propylhexadecyl, 5-ethylhexadecyl, 5-methylhexadecyl, 5-hexadecyloctadecyl, 5-pentadecyloctadecyl, 5-tetradecyloctadecyl, 5-tridecyloctadecyl, 5-dodecyloctadecyl, 5-undecyloctadecyl, 5-decyloctadecyl, 5-nonyloctadecyl, 5-octyloctadecyl, 5-heptyloctadecyl, 5-hexyloctadecyl, 5-pentyloctadecyl, 5-butyloctadecyl, 5-propyloctadecyl, 5-ethyloctadecyl, 5-methyloctadecyl, 5-nonadecyleicosanyl, 5-octadecyleicosanyl, 5-heptadecyleicosanyl, 5-hexadecyleicosanyl, 5-pentadecyleicosanyl,

5-tetradecyleicosanyl, 5-tridecyleicosanyl, 5-dodecyleicosanyl, 5-undecyleicosanyl, 5-decyleicosanyl, 5-nonyleicosanyl, 5-octyleicosanyl, 5-heptyleicosanyl, 5-hexyleicosanyl, 5-pentyleicosanyl, 5-butyleicosanyl, 5-propyleicosanyl, 5-ethyleicosanyl, 5-methyleicosanyl, 5-eicosanyldocosanyl, 5-nonadecyldocosanyl, 5-octadecyldocosanyl, 5-heptadecyldocosanyl, 5-hexadecyldocosanyl, 5-pentadecyldocosanyl, 5-tetradecyldocosanyl, 5-tridecyldocosanyl, 5-undecyldocosanyl, 5-decyldocosanyl, 5-nonyldocosanyl, 5-octyldocosanyl, 5-heptyldocosanyl, 5-hexyldocosanyl, 5-pentyldocosanyl, 5-butyldocosanyl, 5-propyldocosanyl, 5-ethyldocosanyl, 5-methyldocosanyl, 5-tricosanyltetracosanyl, 5-docosanyltetracosanyl, 5-nonadecyltetracosanyl, 5-octadecyltetracosanyl, 5-heptadecyltetracosanyl, 5-hexadecyltetracosanyl, 5-pentadecyltetracosanyl, 5-pentadecyltetracosanyl, 5-tetradecyltetracosanyl, 5-tridecyltetracosanyl, 5-dodecyltetracosanyl, 5-undecyltetracosanyl, 5-decyltetracosanyl, 5-nonyltetracosanyl, 5-octyltetracosanyl, 5-heptyltetracosanyl, 5-hexyltetracosanyl, 5-pentyltetracosanyl, 5-butyltetracosanyl, 5-propyltetracosanyl, 5-ethyltetracosanyl, 5-methyltetracosanyl, δ-heptacosanyloctacosanyl, δ-hexacosanyloctacosanyl, δ-pentacosanyloctacosanyl, 5-tetracosanyloctacosanyl, 5-tricosanyloctacosanyl, 5-docosanyloctacosanyl, 5-nonadecyloctacosanyl, 5-octadecyloctacosanyl, 5-heptadecyloctacosanyl, 5-hexadecyloctacosanyl, 5-hexadecyloctacosanyl, δ-pentadecyloctacosanyl, 5-tetradecyloctacosanyl, 5-tridecyloctacosanyl,

5-dodecyloctacosanyl, 5-undecyloctacosanyl, 5-decyloctacosanyl, 5-nonyloctacosanyl, 5-octyloctacosanyl, 5-heptyloctacosanyl, 5-hexyloctacosanyl, 5-pentyloctacosanyl, 5-butyloctacosanyl, 5-propyloctacosanyl, 5-ethyloctacosanyl, 5-methyloctacosanyl,

in which p is 5, for example

6-hexylheptyl, 6-pentylheptyl, 6-butylheptyl, 6-propylheptyl, 6-ethylheptyl, 6-methylheptyl, 6-heptyloctyl, 6-hexyloctyl, 6-pentyloctyl, 6-butyloctyl, 6-propyloctyl, 6-ethyloctyl, 6-methyloctyl, 6-octylnonyl, 6-heptylnonyl, 6-hexylnonyl, 6-pentylnonyl, 6-butylnonyl, 6-propylnonyl, 6-ethylnonyl, 6-methylnonyl, 6-nonyldecyl, 6-octyldecyl, 6-heptyldecyl, 6-hexyldecyl, 6-pentyldecyl, 6-butyldecyl, 6-propyldecyl, 6-ethyldecyl, 6-methyldecyl, 6-decylundecyl, 6-nonylundecyl, 6-octylundecyl, 6-heptylundecyl, 6-hexylundecyl, 6-pentylundecyl, 6-butylundecyl, 6-propylundecyl, 6-ethylundecyl, 6-methylundecyl, 6-undecyldodecyl, 6-decyldodecyl, 6-nonyldodecyl, 6-octyldodecyl, 6-heptyldodecyl, 6-hexyldodecyl, 6-pentyldodecyl, 6-butyldodecyl, 6-propyldodecyl, 6-ethyldodecyl, 6-methyldodecyl, 6-dodecyltridecyl, 6-undecyltridecyl, 6-decyltridecyl, 6-nonyltridecyl, 6-octyltridecyl, 6-heptyltridecyl, 6-hexyltridecyl, 6-pentyltridecyl, 6-butyltridecyl, 6-propyltridecyl, 6-ethyltridecyl, 6-methyltridecyl, 6-tridecyltetradecyl, 6-undecyltetradecyl, 6-decyltetradecyl, 6-nonyltetradecyl, 6-octyltetradecyl, 6-hetyltetradecyl, 6-hexyltetradecyl, 6-pentyltetradecyl, 6-butyltetradecyl, 6-propyltetradecyl, 6-ethyltetradecyl, 6-methyltetradecyl, 6-pentadecylhexadecyl, 6-tetradecylhexadecyl, 6-tridecylhexadecyl, 6-dodecylhexadecyl, 6-undecylhexadecyl, 6-decylhexadecyl, 6-nonylhexadecyl, 6-octylhexadecyl, 6-heptylhexadecyl, 6-hexylhexadecyl, 6-pentylhexadecyl, 6-butylhexadecyl, 6-propylhexadecyl,

6-ethylhexadecyl, 6-methylhexadecyl, 6-hexadecyloctadecyl, 6-pentadecyloctadecyl, 6-tetradecyloctadecyl, 6-tridecyloctadecyl, 6-dodecyloctadecyl, 6-undecyloctadecyl, 6-decyloctadecyl, 6-nonyloctadecyl, 6-octyloctadecyl, 6-heptyloctadecyl, 6-hexyloctadecyl, 6-pentyloctadecyl, 6-butyloctadecyl, 6-propyloctadecyl, 6-ethyloctadecyl, 6-methyloctadecyl, 6-nonadecyleicosanyl, 6-octadecyleicosanyl, 6-heptadecyleicosanyl, 6-hexadecyleicosanyl, 6-pentadecyleicosanyl, 6-tetradecyleicosanyl, 6-tridecyleicosanyl, 6-dodecyleicosanyl, 6-undecyleicosanyl, 6-decyleicosanyl, 6-nonyleicosanyl, 6-octyleicosanyl, 6-heptyleicosanyl, 6-hexyleicosanyl, 6-pentyleicosanyl, 6-butyleicosanyl, 6-propyleicosanyl, 6-ethyleicosanyl, 6-methyleicosanyl, 6-eicosanyldocosanyl, 6-nonadecyldocosanyl, 6-octadecyldocosanyl, 6-heptadecyldocosanyl, 6-hexadecyldocosanyl, 6-pentadecyldocosanyl, 6-tetradecyldocosanyl, 6-tridecyldocosanyl, 6-undecyldocosanyl, 6-decyldocosanyl, 6-nonyldocosanyl, 6-octyldocosanyl, 6-heptyldocosanyl, 6-hexyldocosanyl, 6-pentyldocosanyl, 6-butyldocosanyl, 6-propyldocosanyl, 6-ethyldocosanyl, 6-methyldocosanyl, 6-tricosanyltetracosanyl, 6-docosanyltetracosanyl, 6-nonadecyltetracosanyl, 6-octadecyltetracosanyl, 6-heptadecyltetracosanyl, 6-hexadecyltetracosanyl, 6-pentadecyltetracosanyl, 6-pentadecyltetracosanyl, 6-tetradecyltetracosanyl, 6-tridecyltetracosanyl, 6-dodecyltetracosanyl, 6-undecyltetracosanyl, 6-decyltetracosanyl, 6-nonyltetracosanyl, 6-octyltetracosanyl, 6-heptyltetracosanyl, 6-hexyltetracosanyl, 6-pentyltetracosanyl, 6-butyltetracosanyl, 6-propyltetracosanyl, 6-ethyltetracosanyl, 6-methyltetracosanyl, θ-heptacosanyloctacosanyl, θ-hexacosanyloctacosanyl, θ-pentacosanyloctacosanyl, θ-tetracosanyloctacosanyl, θ-tricosanyloctacosanyl, θ-docosanyloctacosanyl, 6-nonadecyloctacosanyl, 6-octadecyloctacosanyl, θ-heptadecyloctacosanyl, 6-hexadecyloctacosanyl, 6-hexadecyloctacosanyl, θ-pentadecyloctacosanyl, 6-tetradecyloctacosanyl, θ-tridecyloctacosanyl, 6-dodecyloctacosanyl, 6-undecyloctacosanyl, 6-decyloctacosanyl, 6-nonyloctacosanyl, 6-octyloctacosanyl, 6-heptyloctacosanyl, 6-hexyloctacosanyl, 6-pentyloctacosanyl, 6-butyloctacosanyl, 6-propyloctacosanyl, 6-ethyloctacosanyl, 6-methyloctacosanyl,

in which p is 6, for example

7-heptyloctyl, 7-hexyloctyl, 7-pentyloctyl, 7-butyloctyl, 7-propyloctyl, 7-ethyloctyl, 7-methyloctyl, 7-octylnonyl, 7-heptylnonyl, 7-hexylnonyl, 7-pentylnonyl, 7-butylnonyl, 7-propylnonyl, 7-ethylnonyl, 7-methylnonyl, 7-nonyldecyl, 7-octyldecyl, 7-heptyldecyl, 7-hexyldecyl, 7-pentyldecyl, 7-butyldecyl, 7-propyldecyl, 7-ethyldecyl, 7-methyldecyl, 7-decylundecyl, 7-nonylundecyl, 7-octylundecyl, 7-heptylundecyl, 7-hexylundecyl, 7-pentylundecyl, 7-butylundecyl, 7-propylundecyl, 7-ethylundecyl, 7-methylundecyl, 7-undecyldodecyl, 7-decyldodecyl, 7-nonyldodecyl, 7-octyldodecyl, 7-heptyldodecyl, 7-hexyldodecyl, 7-pentyldodecyl, 7-butyldodecyl, 7-propyldodecyl, 7-ethyldodecyl, 7-methyldodecyl, 7-dodecyltridecyl, 7-undecyltridecyl, 7-decyltridecyl, 7-nonyltridecyl, 7-octyltridecyl, 7-heptyltridecyl, 7-hexyltridecyl, 7-pentyltridecyl, 7-butyltridecyl, 7-propyltridecyl, 7-ethyltridecyl, 7-methyltridecyl, 7-tridecyltetradecyl, 7-undecyltetradecyl, 7-decyltetradecyl, 7-nonyltetradecyl, 7-octyltetradecyl, 7-hetyltetradecyl, 7-hexyltetradecyl, 7-pentyltetradecyl, 7-butyltetradecyl, 7-propyltetradecyl, 7-ethyltetradecyl, 7-methyltetradecyl, 7-pentadecylhexadecyl, 7-tetradecylhexadecyl, 7-tridecylhexadecyl, 7-dodecylhexadecyl, 7-undecylhexadecyl, 7-decylhexadecyl, 7-nonylhexadecyl, 7-octylhexadecyl, 7-heptylhexadecyl, 7-hexylhexadecyl, 7-pentylhexadecyl, 7-butylhexadecyl, 7-propylhexadecyl,

7-ethylhexadecyl, 7-methylhexadecyl, 7-hexadecyloctadecyl, 7-pentadecyloctadecyl, 7-tetradecyloctadecyl, 7-tridecyloctadecyl, 7-dodecyloctadecyl, 7-undecyloctadecyl, 7-decyloctadecyl, 7-nonyloctadecyl, 7-octyloctadecyl, 7-heptyloctadecyl, 7-hexyloctadecyl, 7-pentyloctadecyl, 7-butyloctadecyl, 7-propyloctadecyl, 7-ethyloctadecyl, 7-methyloctadecyl, 7-nonadecyleicosanyl, 7-octadecyleicosanyl, 7-heptadecyleicosanyl, 7-hexadecyleicosanyl, 7-pentadecyleicosanyl, 7-tetradecyleicosanyl, 7-tridecyleicosanyl, 7-dodecyleicosanyl, 7-undecyleicosanyl, 7-decyleicosanyl, 7-nonyleicosanyl, 7-octyleicosanyl, 7-heptyleicosanyl, 7-hexyleicosanyl, 7-pentyleicosanyl, 7-butyleicosanyl, 7-propyleicosanyl, 7-ethyleicosanyl, 7-methyleicosanyl, 7-eicosanyldocosanyl, 7-nonadecyldocosanyl, 7-octadecyldocosanyl, 7-heptadecyldocosanyl, 7-hexadecyldocosanyl, 7-pentadecyldocosanyl, 7-tetradecyldocosanyl, 7-tridecyldocosanyl, 7-undecyldocosanyl, 7-decyldocosanyl, 7-nonyldocosanyl, 7-octyldocosanyl, 7-heptyldocosanyl, 7-hexyldocosanyl, 7-pentyldocosanyl, 7-butyldocosanyl, 7-propyldocosanyl, 7-ethyldocosanyl, 7-methyldocosanyl, 7-tricosanyltetracosanyl, 7-docosanyltetracosanyl, 7-nonadecyltetracosanyl, 7-octadecyltetracosanyl, 7-heptadecyltetracosanyl, 7-hexadecyltetracosanyl, 7-pentadecyltetracosanyl, 7-pentadecyltetracosanyl, 7-tetradecyltetracosanyl, 7-tridecyltetracosanyl, 7-dodecyltetracosanyl, 7-undecyltetracosanyl, 7-decyltetracosanyl,

7-nonyltetracosanyl, 7-octyltetracosanyl, 7-heptyltetracosanyl, 7-hexyltetracosanyl, 7-pentyltetracosanyl, 7-butyltetracosanyl, 7-propyltetracosanyl, 7-ethyltetracosanyl, 7-methyltetracosanyl, 7-heptacosanyloctacosanyl, 7-hexacosanyloctacosanyl, 7-pentacosanyloctacosanyl, 7-tetracosanyloctacosanyl, 7-tricosanyloctacosanyl, 7-docosanyloctacosanyl, 7-nonadecyloctacosanyl, 7-octadecyloctacosanyl, 7-heptadecyloctacosanyl, 7-hexadecyloctacosanyl, 7-hexadecyloctacosanyl, 7-pentadecyloctacosanyl, 7-tetradecyloctacosanyl, 7-tridecyloctacosanyl, 7-dodecyloctacosanyl, 7-undecyloctacosanyl, 7-decyloctacosanyl, 7-nonyloctacosanyl, 7-octyloctacosanyl, 7-heptyloctacosanyl, 7-hexyloctacosanyl, 7-pentyloctacosanyl, 7-butyloctacosanyl, 7-propyloctacosanyl, 7-ethyloctacosanyl, 7-methyloctacosanyl.

According to a preferred embodiment R¹ is a group of the formula III

where

R⁴ is hydrogen or an organyl group, and

^* represents the attachment site to the nitrogen atom of the perylene skeleton.

Preferably, the R⁴ residue is in the ortho position to the attachment site to the nitrogen atom of the perylene skeleton.

Preferably, in the group of the formula III the residue R⁴ is selected from hydrogen, alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkyloxy, aryl, aryloxy, hetaryl, hetaryloxy, hydroxyl, mercapto, COOH, carboxylate, SO3H, sulfonate, NE⁵E⁶ halogen, nitro, acyl and cyano, where E⁵ and E⁶ are identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl and where E⁵ and E⁶ together with the nitrogen atom to which they are bound can also form a 5- to 8-membered heterocycle which may be additionally fused with one, two or three cycloalkyl, heterocycloalkyl, aryl or hetaryl groups, where the heterocycle and, if present, the fused-on groups may each independently bear one, two, three or four substituents selected from among alkyl and the substituents mentioned in the following for the alkyl radicals.

In the residue R⁴ the alkyl radicals can be unsubstituted or substituted by 1 , 2, 3, 4, 5 or more than 5 substituents, preferably selected from among cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, COOH, carboxylate, SO3H, sulfonate, NE⁷E⁸, halogen, nitro, acyl and cyano, where E⁷ and E⁸ are identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl, and the cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals being able to bear 1 , 2, 3, 4 or 5 substituents selected from among alkyl and the substituents mentioned above for the alkyl radicals.

More preferably, in the group of the formula III the residue R⁴ is selected from hydrogen, Ci-Ci₂-alkyl, Ci-Ci₂-alkoxy, COOH, COO(Ci-C₄-alkyl), aryl or polycyclyl.

In a special embodiment, R¹ is a group of the formula III.A

(111. A) where

R⁴ is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, COOH, COOCH₃ or COOC₂H₅,

In a special embodiment, R¹ is a group of the formula III.1

1.1 ) where

M is a divalent metal, a divalent metal atom containing group or a divalent metalloid group, and

# represents the attachment site to the nitrogen atom of the perylene skeleton.

Divalent metals may, for example, be chosen from those of groups 2, 8, 10, 1 1 , 12 and 14 of the Periodic Table. Divalent metals are, for example, Pd(II), Fe(II), Ni(II), Co(II), Cu(II), Zn(II), Cd(II), Ag(II), Mg(II), Sn(II), or Pb (II).

A divalent metal atom containing group may, for example, be chosen from a divalent oxometal, a divalent hydroxymetal, or a divalent halogenometal moiety. In the divalent oxometal moiety, for example, the metal may be chosen from those of groups 4, 5, 7 and 14 of the Periodic Table. Examples of divalent oxometal moieties are V(IV)O, Mn(IV)O, Zr(IV)O, Sn(IV)O Or Ti(IV)O. In a divalent hydroxymetal moiety, the metal may be chosen from those of groups 4, 6, 13, 14 and 15 of the Periodic Table. Examples of divalent hydroxymetal moieties are AI(III)OH, Cr(III)OH, Bi(III)OH, or Zr(IV)(0H)2. In a divalent halogenometal moiety, the metal may be chosen from those of group 13 of the Periodic Table. Examples of divalent halogenometal moieties are for example, for example, AI(III)CI, AI(III)F or In(III)CI.

In divalent metalloid moieties, the metalloid may be chosen from a metalloid of group 14 of the Periodic Table, e.g. silicon. With a tetravalent metalloid, two of the valences may be satisfied by ligands such as hydrogen, hydroxy, halogen, e.g. fluorine or chlorine, alkyl, alkoxy, aryl or aryloxy. Examples of divalent metalloid moieties are SiH2, SiF₂, SiCI₂, Si(OH)₂, Si(alkyl)₂, Si(aryl)₂, Si(alkoxy)₂ and Si(aryloxy)₂. In the formula 111.1 , M is preferably Pd.

In a further special embodiment, R¹ is a group of the formula III.2

(III.2)

where

# represents the attachment site to the nitrogen atom of the perylene skeleton,

R⁵ and R⁶ are independently hydrogen or unsubstituted or substituted alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the cycloalkyl, heterocycloalkyl, aryl or hetaryl groups each can also be part of a condensed ring system.

Preferably, R¹ is a group of the formula

In a preferred alternative embodiment, two substituents R¹ form a divalent bridging group X between two moieties of the formula Ia, wherein X has from 1 to 20 bridge atoms between the flanking bonds. Thus, two moieties of the formula Ia can be linked by a bridging group X as follows:

Preferably, X comprises at least one carbocycle and/or at least one heterocycle. The carbocycle and the heterocycles can be part of a fused ring system having 1 , 2 or 3 further rings that are selected from cycloalkyl, heterocycloalkyl, aryl and/or hetaryl. Fused-on rings are preferably unsubstituted or bear 1 , 2, 3 or 4 substituents selected from among alkyl, alkoxy, cycloalkyl, aryl, halogen, hydroxy, mercapto, COOH, carboxylate, SO3H, sulfonate, NE³E⁴, alkylene-NE³E⁴, nitro and cyano, where E³ and E⁴ independently are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

Suitable linking groups X are:

arylene, e.g. phenylene like 1 ,2-phenylene, 1 ,3-phenylene, 1 ,4-phenylene, naphthylen, e.g. 1 ,4-naphthylene, 1 ,5-naphthylene, 1 ,8-naphthylene etc. The arylene group is unsubstituted or substituted by one, two, three, four or five identical or different substituents. Suitable substituents are e.g. Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, Cs-Cs-cycloalkyl, phenyl, Ci-C2o-alkoxy, fluorine, chlorine, bromine, cyano, OH, nitro or NE³E⁴, where E³ and E⁴ independently are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

arylene-alkylene, e.g. C6-Ci8-arylene-Ci-Ci2-alkylene. The arylene-alkylene group is unsubstituted or substituted by one, two, three, four or more than four identical or different substituents. Suitable substituents are e.g. Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, Cs-Cs-cycloalkyl, phenyl, Ci-C2o-alkoxy, fluorine, chlorine, bromine, cyano, OH, nitro or NE³E⁴, where E³ and E⁴ independently are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

alkylene-arylene-alkylene, e.g. Ci-Ci2-alkylen-C6-Cis-arylene-Ci-Ci2-alkylene. The alkylene-arylene-alkylene group is unsubstituted or substituted by one, two, three, four or more than four identical or different substituents. Suitable substituents are e.g. Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, Cs-Cs-cycloalkyl, phenyl, Ci-C2o-alkoxy, fluorine, chlorine, bromine, cyano, OH, nitro or NE³E⁴, where E³ and E⁴ independently are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

- polycyclylene. The polycyclylene group is unsubstituted or substituted by one, two, three, four or more than four identical or different substituents. Suitable substituents are e.g. Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, Cs-Cs-cycloalkyl, phenyl, Ci-C2o-alkoxy, fluorine, chlorine, bromine, cyano, OH, nitro or NE³E⁴, where E³ and E⁴ independently are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

A preferred bridging group X is a group of the formula

Some especially preferred oligocondensed perylene bisimides are as follows:

Preferably, R² and R³ are selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl or halogen.

A further preferred embodiment are oligocondensed perylene bisimides, comprising one outer moiety of the formula Ia and one outer moiety of the formula Ib, wherein R² and R³ are both hydrogen or R² and R³ are both chlorine.

A special embodiment are diperylene bisimides

wherein R^a, R^b and R¹ have the afore-mentioned meanings. Especially preferred are compounds of the formulae:

(1 ) (2)

(3)

(6)

(9)

formulae (10), (11), (12): n = 1 -12

formulae (13), (14), (15): n = 1 - 12

formulae (16), (17), (18): n = 1 - 12

formulae (19), (20), (21): n = 1 -12

formulae (22), (23), (24): n = 1 - 12

formulae (25), (26), (27): n = 1 - 12

(28)

Ĩ31) A further object of the invention is to provide a process for preparing oligocondensed perylene bisimides, comprising two outer moieties of the formula Ia

R^a

#

R N

#

O N O

R^b (Ia)

or one outer moiety of the formula Ia and one outer moiety of the formula Ib

and - n inner moieties selected from moieties of the formulae (Ic) and (Id)

where

#, R^a, R^b, n, R² and R³ are defined as in any of claims 1 to 5 or 8 and

R¹ is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl or polycyclyl, wherein oligocondensed perylene bisimides, comprising two outer moieties of the formula IVa

(IVa) or one outer moiety of the formula IVa and one outer moiety of the formula Ib

are subjected to a reaction with an amine of the formula R¹-NH2 in the presence of a palladium catalyst comprising at least one phosphorus-containing ligand.

A further object of the invention is to provide a process for preparing oligocondensed perylene bisimides, comprising

two outer moieties of the formula Ia

(Ia)

or one outer moiety of the formula Ia and one outer moiety of the formula Ib

and

n inner moieties selected from moieties of the formulae (Ic) and (Id)

where

#, R^a, R^b, n, R² and R³ are defined as in any of claims 1 to 5 or 8 and

two substituents R¹ form a divalent bridging group X between two moieties of the formula Ia, wherein X has from 1 to 20 bridge atoms between the flanking bonds,

wherein oligocondensed perylene bisimides, comprising

two outer moieties of the formula IVa

(IVa)

or one outer moiety of the formula IVa and one outer moiety of the formula Ib

are subjected to a reaction with an amine of the formula H2N-X-NH2 in the presence of a palladium catalyst comprising at least one phosphorus-containing ligand.

The cross coupling reaction of aryl halides with primary or secondary amines in the presence of a palladium catalyst comprising at least one phosphorus-containing ligand is known as Buchwald-Hartwig reaction.

The Buchwald-Hartwig cross-coupling normally takes place in the presence of a phosphorus-containing ligand, especially of a monodentate or bidentate phosphine ligand. Preferred ligands on the palladium are bulky, monodentate or bidentate phosphines, such as triphenylphosphine, tri(o-tolyl)phosphine, tri(cyclohexyl)phosphine, BINAP (2,2'-bis-(diphenylphosphino)-1 ,1 '-binaphthyl) or the

Buchwald phosphines. The ligand may be present in the palladium compound or be added separately. Suitable palladium compounds include tris(dibenzylideneacetone)dipalladium(0), palladium(ll) bis(o-tolyl)phosphine chloride and palladium(ll) acetate. The Buchwald-Hartwig cross-coupling normally takes place in an organic solvent. Suitable organic solvents are aromatic hydrocarbons, such as benzene or toluene, halogenated aromatic hydrocarbons, such as chlorobenzene, halogenated hydrocarbons, such as dichloromethane, trichloromethane, dichloroethane, ethers, such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, or amides, such as dimethylformamide or N-methylpyrrolidone, and mixtures thereof.

The reaction is usually carried out in the presence of a strong base, e.g. an alkoxide, like potassium alkoxide, sodium alkoxide, lithium alkoxide. A preferred base is NaOt-Bu. Further suitable bases are hydrides, like potassium hydride and sodium hydride, and amides, like lithium bis(trimetylsilyl)amid.

The Buchwald coupling reaction can be carried out under normal conditions or with use of microwaves.

The reaction temperature is preferably from 0 to 220⁰C, more preferably 20 to 200⁰C, especially 50 to 180°C.

The reaction can be carried out under inert atmosphere, e.g. under nitrogen atmosphere.

The reaction can be carried out under ambient pressure or higher pressure. A suitable pressure range is from about 0.8 to 10 bar.

A further object of the invention is a composition of oligocondensed perylene bisimides, obtainable by a process as defined above.

The synthesis of tetrachloro oligoperylene bisimides and dichloro oligoperylene bisimides can be performed by an Ullmann type reaction as disclosed in principle by H. Quian, Z. Wang, W. Yue and D. Zhu in J. Am. Chem. Soc. 2007, 129, pages 10664- 10665. As mentioned before, tetrachloro oligoperylene bisimides and dichloro oligoperylene bisimides are especially suitable as intermediates in the synthesis of the oligocondensed perylene bisimides of the invention.

The Ullmann type reaction of two tetrachloro perylene bisimides leads to the formation of three new C-C bonds by a combination of Ullmann reaction and C-H transformation. Thus the cleavage of four C-Cl bonds and the participation of the ortho sp² C-H bond leads to triply linked oligoperylene bisimides. Depending on the reaction conditions, especially the temperature and/or the reaction time, also dehalogenated products can be obtained. Scheme 6 shows the synthesis of tetrachloro diperylene bisimide and dichloro diperylene bisimide from a tetrachloro perylene bisimide.

Scheme 6:

Depending on the reaction conditions, also oligoperylene bisimides, e.g. triperylene bisimides, tetraperylene bisimides, pentaperylene bisimides, and hexaperylene bisimides can be obtained. It is also possible to prepare higher oligoperylene bisimides from lower oligoperylene bisimides, e.g. tetraperylene bisimides from diperylene bisimides. Again, also dehalogenated products can be obtained.

The aforementioned Ullmann type reaction usually leads to reaction mixtures comprising more than one oligoperylene bisimide. A person skilled in the art can obtain reaction mixtures containing the desired products by variation of the reaction parameters. The degree of condensation and dehalogenation depends on the reaction temperature and/or the reaction time. E.g., the longer the reaction time the more higher condensated products are obtained, the higher the temperature, the more dehalogenation is obtained. The desired products can be separated from the reaction mixtures by known methods, preferably by column chromatography. Suitable solvents for the column chromatography are aliphatic, cycloaliphatic and aromatic hydrocarbons, such as pentane, hexane, heptane, octane, ligroine, petroleum ether, cyclohexane, dekaline, toluene or xylene, halogenated solvents, such as dichloromethane, chloroform, CCU, dichloroethane or chlorbenzol, and mixtures thereof. Preferred are mixtures of petroleum ether and dichloromethane.

Suitable solvents for the Ullmann reaction are polar aprotic solvents, like dimethylsulfoxide (DMSO), acetonitrile, N,N-dimethylformamide,

N,N-dimethylacetamide, N-methylpyrrolidone, etc. Preferred is DMSO.

As copper reagent in the Ullmann reaction preferably CuI is employed. The CuI is preferably employed in an amount of at least one mol per mol of tetrachloroperylene bisimide. The molar ratio of CuI and tetrachloroperylene bisimide is preferably in a range of from 0.9 : 1 to 20 : 1 , more preferably 1 : 1 to 10 : 1.

As preferred ligand for the Ullmann reaction, L-proline is used.

The reaction is usually carried out in the presence of a base, e.g. an alkaline carbonate, preferably potassium carbonate.

The reaction temperature is preferably from 20 to 120⁰C, more preferably 50 to 1 10⁰C, especially 700 to 100°C.

Thus, it is e.g. possible to obtain the following products and structural isomers thereof:

n = 0,1 ,2,3,4,5 or 6.

The degree of dehalogenation depends on the reaction temperature and/or the reaction time. The higher the temperature, the more dehalogenation is obtained.

The inventive oligocondensed perylene bisimides exhibit absorption in the UVA/IS region.

The inventive oligocondensed perylene bisimides are suitable for a series of uses, such as the general coloring of organic and inorganic materials, for example of coatings, printing inks and plastics, for preparing aqueous polymer dispersions which absorb in the UV/VIS region of the electromagnetic spectrum, for obtaining markings and inscriptions which absorb infrared light, but are invisible to the human eye, as infrared absorbers for heat management and as active components in photovoltaics.

The oligocondensed perylene bisimides are particularly advantageously suitable for use in organic photovoltaics (OPVs). In principle, these compounds are suitable for use in dye-sensitized solar cells. However, preference is given to their use in solar cells which are characterized by diffusion of excited states (exciton diffusion). In this case, one or both of the semiconductor materials utilized is notable for a diffusion of excited states. Also suitable is the combination of at least one semiconductor material which is characterized by diffusion of excited states with polymers which permit conduction of the excited states along the polymer chain. In the context of the invention, such solar cells are referred to as excitonic solar cells. The direct conversion of solar energy to electrical energy in solar cells is based on the internal photo effect of a semiconductor material, i.e. the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a p-n transition or a Schottky contact. An exciton can form, for example, when a photon penetrates into a semiconductor and excites an electron to transfer from the valence band into the conduction band. In order to generate current, the excited state generated by the absorbed photons must, however, reach a p-n transition in order to generate a hole and an electron which then flow to the anode and cathode. The photovoltage thus generated can bring about a photocurrent in an external circuit, through which the solar cell delivers its power. The semiconductor can absorb only those photons which have an energy which is greater than its band gap. The size of the semiconductor band gap thus determines the proportion of sunlight which can be converted to electrical energy. The excitonic solar cells described consist normally of two absorbing materials with different band gaps in order to very effectively utilize the solar energy. Most organic semiconductors have exciton diffusion lengths of up to 10 nm. There is still a need here for organic semiconductors through which the excited state can be passed on over very large distances. It has now been found that, surprisingly, the compounds of the general formula I described above are particularly advantageously suitable for use in excitonic solar cells.

Suitable organic solar cells generally have a layer structure and generally comprise at least the following layers: anode, photoactive layer and cathode. These layers generally consist of a substrate customary, therefore. The structure of organic solar cells is described, for example, in US 2005/0098726 A1 and US 2005/0224905 A1 , which are fully incorporated here by reference.

Suitable substrates are, for example, oxidic materials (such as glass, quartz, ceramic, Siθ2, etc.), polymers (e.g. polyvinyl chloride, polyolefins, such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth)acrylates, polystyrene and mixtures and composites thereof) and combinations thereof.

Suitable electrodes (cathode, anode) are in principle metals (preferably of groups 8, 9, 10 or 11 of the Periodic Table, e.g. Pt, Au, Ag, Cu, Al, In, Mg, Ca), semiconductors (e.g. doped Si, doped Ge, indium tin oxide (ITO), gallium indium tin oxide (GITO), zinc indium tin oxide (ZITO), etc.), metal alloys (e.g. based on Pt, Au, Ag, Cu, etc., especially Mg/Ag alloys), semiconductor alloys, etc. The anode used is preferably a material essentially transparent to incident light. This includes, for example, ITO, doped ITO, ZnO, Tiθ2, Ag, Au, Pt. The cathode used is preferably a material which essentially reflects the incident light. This includes, for example, metal films, for example of Al, Ag, Au, In, Mg, Mg/AI, Ca, etc. For its part, the photoactive layer comprises at least one or consists of at least one layer which comprises, as an organic semiconductor material, at least one compound which is selected from compounds of the formulae I and Il as defined above. In one embodiment, the photoactive layer comprises at least one organic acceptor material. In addition to the photoactive layer, there may be one or more further layers, for example a layer with electron-conducting properties (ETL, electron transport layer) and a layer which comprises a hole-conducting material (hole transport layer, HTL) which need not absorb, exciton- and hole-blocking layers (e.g. EBLs) which should not absorb, multiplication layers. Suitable exciton- and hole-blocking layers are described, for example, in US 6,451 ,415.

Suitable exciton blocker layers are, for example, bathocuproins (BCPs), 4,4',4"-tris(N-(3-methylphenyl)-N-phenylamino)triphenylamine (m-MTDATA) or polyethylenedioxythiophene (PEDOT), as described in US 7,026,041.

The inventive excitonic solar cells are based on photoactive donor-acceptor heterojunctions. When at least one compound of the formula (I) is used as the HTM, the corresponding ETM must be selected such that, after excitation of the compounds, a rapid electron transfer to the ETM takes place. Suitable ETMs are, for example, C60 and other fullerenes, perylene-3,4:9,10-bis(dicarboximides), PTCDIs, etc. When at least one compound of the formula (I) is used as the ETM, the complementary HTM must be selected such that, after excitation of the compound, a rapid hole transfer to the HTM takes place. The heterojunction may have a flat configuration (cf. Two layer organic photovoltaic cell, C. W. Tang, Appl. Phys. Lett., 48 (2), 183-185 (1986) or N. Karl, A. Bauer, J. Holzapfel, J. Marktanner, M. Mobus, F. Stolzle, MoI. Cryst. Liq. Cryst, 252, 243-258 (1994).) or be implemented as a bulk heterojunction (or interpenetrating donor-acceptor network; cf., for example, C. J. Brabec, N. S. Sariciftci, J. C. Hummelen, Adv. Funct. Mater., 1 1 (1 ), 15 (2001 ).). The photoactive layer based on a heterojunction between at least one compound of the formula (I) and an HTL or ETL can be used in solar cells with MiM, pin, pn, Mip or Min structure (M=metal, p=p- doped organic or inorganic semiconductor, n=n-doped organic or inorganic semiconductor, i=intrinsically conductive system of organic layers; cf., for example, J. Drechsel et al., Org. Eletron., 5 (4), 175 (2004) or Maennig et al., Appl. Phys. A 79, 1-14 (2004)). It can also be used in tandem cells, as described by P. Peumnas, A. Yakimov, S. R. Forrest in J. Appl. Phys, 93 (7), 3693-3723 (2003) (cf. patents

US 04461922, US 06198091 and US 06198092). It can also be used in tandem cells composed of two or more MiM, pin, Mip or Min diodes stacked on one another (cf. patent application DE 103 13 232.5) (J. Drechsel et al., Thin Solid Films, 451452, 515- 517 (2004)). Thin layers of the compounds and of all other layers can be produced by vapor deposition under reduced pressure or in inert gas atmosphere, by laser ablation or by solution- or dispersion-processible methods, such as spin-coating, knife-coating, casting methods, spraying, dip-coating or printing (e.g. inkjet, flexographic, offset, gravure; intaglio, nanoimprinting). The layer thicknesses of the M, n, i and p layers are typically from 10 to 1000 nm, preferably from 10 to 400 nm.

The substrates used are, for example, glass, metal foils or polymer films which are generally coated with a transparent conductive layer (for example Snθ2:F, Snθ2:ln, ZnO:AI, carbon nanotubes, thin metal layers).

In addition to the compounds of the general formula (I), the following semiconductor materials are suitable for use in organic photovoltaics:

Acenes, such as anthracene, tetracene, pentacene, each of which may be substituted or unsubstituted. Substituted acenes preferably comprise at least one substituent selected from electron-donating substituents (e.g. alkyl, alkoxy, ester, carboxylate or thioalkoxy), electron-withdrawing substituents (e.g. halogen, nitro or cyano) and combinations thereof. These include 2,9-dialkylpentacenes and

2,10-dialkylpentacenes, 2,10-dialkoxypentacenes, 1 ,4,8,11-tetraalkoxypentacenes and rubrene (5,6,11 ,12-tetraphenylnaphthacene). Suitable substituted pentacenes are described in US 2003/0100779 and US 6,864,396, which are incorporated here by reference. A preferred acene is rubrene (5,6,11 ,12-tetraphenylnaphthacene).

Phthalocyanines, for example phthalocyanines which bear at least one halogen substituent, such as hexadecachlorophthalocyanines and hexadecafluorophthalo- cyanines, metal-free phthalocyanines or phthalocyanines comprising divalent metals or metal atom-containing groups, especially those of titanyloxy, vanadyloxy, iron, copper, zinc, etc. Suitable phthalocyanines are especially copper phthalocyanine, zinc phthalocyanine, metal-free phthalocyanine, copper hexadecachlorophthalocyanine, zinc hexadecachlorophthalocyanine, metal-free hexadecachlorophthalocyanine, copper hexadecafluorophthalocyanine, hexadecafluorophthalocyanine or metal-free hexadecafluorophthalocyanine.

Porphyrins, for example 5,10,15,20-tetra(3-pyridyl)porphyrin (TpyP).

Liquid-crystalline (LC) materials, for example coronenes, such as hexabenzocoronene (HBC-PhC12), coronenediimides, or triphenylenes, such as 2,3,6,7,10,1 1-hexahexylthiotriphenylene (HTT6), 2,3,6,7,10,11-hexakis(4-n- nonylphenyl)-triphenylene (PTP9) or 2,3,6,7,10,11-hexakis(undecyloxy)triphenylene (HAT1 1 ). Particular preference is given to liquid-crystalline materials which are discotic.

Thiophenes, oligothiophenes and substituted derivatives thereof. Suitable oligothiophenes are quaterthiophenes, quinquethiophenes, sexithiophenes, α,ω-di(Ci-C8)alkyloligothiophenes such as α,ω-dihexylquaterthiophenes, α,ω-dihexylquinquethiophenes and α,ω-dihexylsexithiophenes, poly(alkylthiophenes) such as poly(3-hexylthiophene), bis(dithienothiophenes), anthradithiophenes and dialkylanthradithiophenes such as dihexylanthradithiophene, phenylene-thiophene (P-T) oligomers and derivatives thereof, especially α,ω-alkyl-substituted phenylene- thiophene oligomers.

Also suitable are compounds of the α,α'-bis(2,2-dicyanovinyl)quinquethiophene (DCV5T) type, (3-(4-octylphenyl)-2,2'-bithiophene) (PTOPT), poly(3-(4'-(1 ,4,7- trioxaoctyl)phenyl)thiophene) (PEOPT), poly(3-(2'-methoxy-5'-octylphenyl)thiophene) (POMeOPT), poly(3-octylthiophene) (P3OT), poly(pyridopyrazinevinylene)- polythiophene blends, such as EHH-PpyPz, PTPTB copolymers, BBL, F8BT, PFMO; see Brabec C, Adv. Mater., 2996, 18, 2884, (PCPDTBT) poly[2,6-(4,4-bis(2- ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-4,7-(2,1 ,3-benzothiadiazole)].

Paraphenylenevinylene and paraphenylenevinylene-comprising oligomers and polymers, for example polyparaphenylenevinylene, MEH-PPV (poly(2-methoxy-5-(2'- ethylhexyloxy)-1 ,4-phenylenevinylene)), MDMO-PPV (poly(2-methoxy-5-(3',7'- dimethyloctyloxy)-1 ,4-phenylenevinylene)), PPV, CN-PPV (with various alkoxy derivatives).

Phenyleneethynylene/phenylenevinylene (PPE-PPV) hybrid polymers.

Polyfluorenes and alternating polyfluorene copolymers, for example with 4,7-dithien-2'- yl-2,1 ,3-benzothiadiazole; also suitable are poly(9,9'-dioctylfluorene-co- benzothiadiazole) (FeBT), poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'- phenyl-1 ,4-phenylenediamine) (PFB).

Polycarbazoles, i.e. carbazole-comprising oligomers and polymers, such as (2,7) and (3,6).

Polyanilines, i.e. aniline-comprising oligomers and polymers, such as (2,7) and (3,6). Triarylamines, polytriarylamines, polycyclopentadienes, polypyrroles, polyfurans, polysiloles, polyphospholes, TPD, CBP, spiro-MeOTAD.

Fullerenes, especially C60 and derivatives thereof, such as PCBM (= [6,6]-phenyl-C6i- butyric acid methyl ester). In such cells, the fullerene derivative is a hole conductor.

Copper(l) iodide, copper(l) thiocyanate.

p-n-Mixed materials, i.e. donor and acceptor in one material, polymer, block polymer, polymers with C60s, C60 azo dyes, triad carotenoid-porphyrin-quinoid LC donor/acceptor systems, as described by S. Kelly in Adv. Mater. 2006, 18, 1754.

All aforementioned semiconductor materials may also be doped. Examples of dopants for p-semiconductors: 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F₄-TCNQ), etc.

The inventive (novel) compounds (I) are also suitable particularly advantageously as organic semiconductors. They function generally as n-semiconductors. When the oligocondensed perylene bisimides used in accordance with the invention are combined with other semiconductors and the position of the energy levels causes the other semiconductors to function as n-semiconductors, the compounds (I) can also function as p-semiconductors in exceptional cases. This is the case, for example, for the combination with cyano-substituted perylenetetracarboximides. The oligocondensed perylene bisimides are notable for their air stability. They also possess a high charge transport mobility and have a high on/off ratio. They are suitable in a particularly advantageous manner for organic field-effect transistors. The inventive compounds are advantageously suitable for preparing integrated circuits (ICs) for which the n-channel MOSFETs (metal oxide semiconductor field-effect transistors) customary to date are used. These are CMOS-like semiconductor units, for example for microprocessors, microcontrollers, static RAM and other digital logic units. For the production of semiconductor materials, the processes according to the invention can be processed further by one of the following processes: printing (offset, flexographic, gravure, screen, inkjet, electrophotography), evaporation, laser transfer, photolithography, dropcasting. They are suitable in particular for use in displays (especially large-area and/or flexible displays) and RFID tags.

The inventive compounds are also suitable particularly advantageously for data storage, in diodes, especially in OLEDs, in photovoltaics, as UV absorbers, as optical brighteners and as invisible labels. The inventive compounds are also suitable particularly advantageously in a light- collecting plastics part which, if appropriate, is combined with a solar cell and as a pigment dye in electrophoretic displays.

The inventive compounds are also particularly suitable as fluorescence emitters in OLEDs, in which they are excited either by electroluminescence or by an appropriate phosphorescence emitter via Forster energy transfer (FRET).

The inventive compounds are also particularly suitable in displays which switch colors on and off based on an electrophoretic effect via charged pigment dyes. Such electrophoretic displays are described, for example, in US 2004/0130776.

The inventive compounds are also particularly suitable for use in a light-collecting plastics part which absorbs light over a large surface and at whose edges the light is emitted after multiple refraction (so-called LISAs). Such LISAs may have, at the edges, solar cells, for example silicon solar cells or organic solar cells, which convert the concentrated light to electrical energy. A combination of light-collecting plastics with solar cells is described, for example, in US 4,110,123.

The inventive compounds are also particularly suitable in chemoluminescence applications. These include so-called "glow sticks". They can be produced by dissolving at least one compound of the formula (I), for example in an alkyl phthalate. The chemoluminescence can be induced by mixing an oxalic ester with hydrogen peroxide, for example, after these two initially separate components have been mixed by breaking a piece of glass. The resulting reaction energy leads to the excitation and fluorescence of the dyes. Such glow sticks can be used as emergency light, for example for angling, in lifejackets for emergency sea rescue or other safety applications.

The invention further provides organic field-effect transistors comprising a substrate comprising at least one gate structure, a source electrode and a drain electrode and at least one compound of the formula I as defined above as an n-semiconductor. The invention further provides substrates comprising a multitude of organic field-effect transistors, wherein at least some of the field-effect transistors comprise at least one compound of the formula I as defined above as an n-semiconductor. The invention also provides semiconductor units which comprise at least one such substrate. A specific embodiment is a substrate with a pattern (topography) of organic field-effect transistors, each transistor comprising

an organic semiconductor disposed on the substrate; - a gate structure for controlling the conductivity of the conductive channel; and conductive source and drain electrodes at the two ends of the channel;

the organic semiconductor consisting of at least one compound of the formula (I) or comprising a compound of the formula (I). In addition, the organic field-effect transistor generally comprises a dielectric.

A further specific embodiment is a substrate having a pattern of organic field-effect transistors, each transistor forming an integrated circuit or being part of an integrated circuit and at least some of the transistors comprising at least one compound of the formula (I).

Suitable substrates are in principle the materials known for this purpose. Suitable substrates comprise, for example, metals (preferably metals of groups 8, 9, 10 or 1 1 of the Periodic Table, such as Au, Ag, Cu), oxidic materials (such as glass, quartz, ceramics, Siθ2), semiconductors (e.g. doped Si, doped Ge), metal alloys (for example based on Au, Ag, Cu, etc.), semiconductor alloys, polymers (e.g. polyvinyl chloride, polyolefins, such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyimides, polyurethanes, polyalkyl (meth)acrylates, polystyrene and mixtures and composites thereof), inorganic solids (e.g. ammonium chloride), paper and combinations thereof. The substrates may be flexible or inflexible, and have a curved or planar geometry, depending on the desired use.

A typical substrate for semiconductor units comprises a matrix (for example a quartz or polymer matrix) and, optionally, a dielectric top layer.

Suitable dielectrics are SiU2, polystyrene, poly-α-methylstyrene, polyolefins (such as polypropylene, polyethylene, polyisobutene), polyvinylcarbazole, fluorinated polymers (e.g. Cytop, CYMM), cyanopullulans, polyvinylphenol, poly-p-xylene, polyvinyl chloride, or polymers crosslinkable thermally or by atmospheric moisture. Specific dielectrics are "self-assembled nanodielectrics", i.e. polymers which are obtained from monomers comprising SiCI functionalities, for example CbSiOSiCb, CbSi-(CH2)6-SiCb, CbSi-(CH2)i2-SiCb, and/or which are crosslinked by atmospheric moisture or by addition of water diluted with solvents (see, for example, Faccietti Adv. Mat. 2005, 17, 1705-1725). Instead of water, it is also possible for hydroxyl-containing polymers, such as polyvinylphenol or polyvinyl alcohol or copolymers of vinylphenol and styrene to serve as crosslinking components. It is also possible for at least one further polymer to be present during the crosslinking operation, for example polystyrene, which is then also crosslinked (see Facietti, US patent application 2006/0202195).

The substrate may additionally have electrodes, such as gate, drain and source electrodes of OFETs, which are normally localized on the substrate (for example deposited onto or embedded into a nonconductive layer on the dielectric). The substrate may additionally comprise conductive gate electrodes of the OFETs, which are typically arranged below the dielectric top layer (i.e. the gate dielectric).

In a specific embodiment, an insulator layer (gate insulating layer) is present on at least part of the substrate surface. The insulator layer comprises at least one insulator which is preferably selected from inorganic insulators, such as Siθ2, SiN, etc., ferroelectric insulators, such as AI2O3, Ta2θs, La2θs, Tiθ2, Y2O3, etc., organic insulators, such as polyimides, benzocyclobutene (BCB), polyvinyl alcohols, polyacrylates, etc., and combinations thereof.

Suitable materials for source and drain electrodes are in principle electrically conductive materials. These include metals, preferably metals of groups 8, 9, 10 or 11 of the Periodic Table, such as Pd, Au, Ag, Cu, Al, Ni, Cr, etc. Also suitable are conductive polymers, such as PEDOT (= poly(3,4-ethylenedioxythiophene)); PSS (= poly(styrenesulfonate)), polyaniline, surface-modified gold, etc. Preferred electrically conductive materials have a specific resistance of less than 10^"3 ohm x meter, preferably less than 10^"4 ohm x meter, especially less than 10^"6 or 10^"7 ohm x meter.

In a specific embodiment, drain and source electrodes are present at least partly on the organic semiconductor material. It will be appreciated that the substrate may comprise further components as used customarily in semiconductor materials or ICs, such as insulators, resistors, capacitors, conductor tracks, etc.

The electrodes may be applied by customary processes, such as evaporation, lithographic processes or another structuring process.

The semiconductor materials may also be processed with suitable auxiliaries (polymers, surfactants) in disperse phase by printing.

In a first preferred embodiment, the deposition of at least one compound of the general formula I (and if appropriate further semiconductor materials) is carried out by a gas phase deposition process (physical vapor deposition, PVD). PVD processes are performed under high-vacuum conditions and comprise the following steps: evaporation, transport, deposition. It has been found that, surprisingly, the compounds of the general formula I are suitable particularly advantageously for use in a PVD process, since they essentially do not decompose and/or form undesired by-products. The material deposited is obtained in high purity. In a specific embodiment, the deposited material is obtained in the form of crystals or comprises a high crystalline content. In general, for the PVD, at least one compound of the general formula I is heated to a temperature above its evaporation temperature and deposited on a substrate by cooling below the crystallization temperature. The temperature of the substrate in the deposition is preferably within a range from about 20 to 250⁰C, more preferably from 50 to 200⁰C. It has been found that, surprisingly, elevated substrate temperatures in the deposition of the compounds of the formula I can have advantageous effects on the properties of the semiconductor elements achieved.

The resulting semiconductor layers generally have a thickness which is sufficient for ohmic contact between source and drain electrodes. The deposition can be effected under an inert atmosphere, for example under nitrogen, argon or helium.

The deposition is effected typically at ambient pressure or under reduced pressure. A suitable pressure range is from about 10^"7 to 1.5 bar.

The compound of the formula (I) is preferably deposited on the substrate in a thickness of from 10 to 1000 nm, more preferably from 15 to 250 nm. In a specific embodiment, the compound of the formula I is deposited at least partly in crystalline form. For this purpose, especially the above-described PVD process is suitable. Moreover, it is possible to use previously prepared organic semiconductor crystals. Suitable processes for obtaining such crystals are described by R. A. Laudise et al. in "Physical Vapor Growth of Organic Semi-Conductors", Journal of Crystal Growth 187 (1998), pages 449-454, and in "Physical Vapor Growth of Centimeter-sized Crystals of α-Hexathiophene", Journal of Crystal Growth 1982 (1997), pages 416-427, which are incorporated here by reference.

The compounds of the general formula (I) can also particularly advantageously be processed from solution. In a second preferred embodiment, the deposition of at least one compound of the general formula (I) (and if appropriate further semiconductor materials) is therefore effected by spin-coating. The oligocondensed perylene bisimides should also be suitable for producing semiconductor elements, especially OFETs or based on OFETs, by a printing process. It is possible for this purpose to use customary printing processes (inkjet, flexographic, offset, gravure, intaglio printing, nanoprinting). Preferred solvents for the use of the oligocondensed perylene bisimides in a printing process are aromatic solvents, such as toluene, xylene, etc. It is also possible to add thickening substances, such as polymers, for example polystyrene, etc., to these "semiconductor inks". In this case, the dielectrics used are the aforementioned compounds.

In a preferred embodiment, the inventive field-effect transistor is a thin-film transistor (TFT). In a customary construction, a thin-film transistor has a gate electrode disposed on the substrate, a gate insulator layer disposed thereon and on the substrate, a semiconductor layer disposed on the gate insulator layer, an ohmic contact layer on the semiconductor layer, and a source electrode and a drain electrode on the ohmic contact layer.

In a preferred embodiment, the surface of the substrate, before the deposition of at least one compound of the general formula (I) (and if appropriate of at least one further semiconductor material), is subjected to a modification. This modification serves to form regions which bind the semiconductor materials and/or regions on which no semiconductor materials can be deposited. The surface of the substrate is preferably modified with at least one compound (C1 ) which is suitable for binding to the surface of the substrate and to the oligocondensed perylene bisimides. In a suitable embodiment, a portion of the surface or the complete surface of the substrate is coated with at least one compound (C1 ) in order to enable improved deposition of at least one compound of the general formula (I) (and if appropriate further semiconductive compounds). A further embodiment comprises the deposition of a pattern of compounds of the general formula (C1 ) on the substrate by a corresponding production process. These include the mask processes known for this purpose and so-called "patterning" processes, as described, for example, in US 1 1/353934, which is incorporated here fully by reference.

Suitable compounds of the formula (C1 ) are capable of a binding interaction, both with the substrate and with at least one semiconductor compound of the general formula I. The term "binding interaction" comprises the formation of a chemical bond (covalent bond), ionic bond, coordinative interaction, van der Waals interactions, e.g. dipole- dipole interactions etc., and combinations thereof. Suitable compounds of the general formula (C1 ) are:

silanes, phosphonic acids, carboxylic acids, hydroxamic acids, such as alkyltrichlorosilanes, e.g. n-octadecyltrichlorosilane; compounds with trialkoxysilane groups, e.g. alkyltrialkoxysilanes, such as n-octadecyltrimethoxy- silane, n-octadecyltriethoxysilane, n-octadecyltri(n-propyl)oxysilane, n-octadecyltri(isopropyl)oxysilane; trialkoxyaminoalkylsilanes, such as triethoxyaminopropylsilane and N-[(3-triethoxysilyl)propyl]ethylenediamine; trialkoxyalkyl 3-glycidyl ether silanes, such as triethoxypropyl 3-glycidyl ether silane; trialkoxyallylsilanes, such as allyltrimethoxysilane; trialkoxy(isocyanato- alkyl)silanes; trialkoxysilyl(meth)acryloyloxyalkanes and trialkoxysilyl(meth)- acrylamidoalkanes, such as 1-triethoxysilyl-3-acryloyloxypropane;

amines, phosphines and sulfur-comprising compounds, especially thiols.

The compound (C1 ) is preferably selected from alkyltrialkoxysilanes, especially n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane; hexaalkyldisilazanes, and especially hexamethyldisilazane (HMDS); Cs-Cso-alkylthiols, especially hexadecanethiol; mercaptocarboxylic acids and mercaptosulfonic acids, especially mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, 3-mercapto- 1-propanesulfonic acid and the alkali metal and ammonium salts thereof.

Various semiconductor architectures comprising the inventive semiconductors are also conceivable, for example top contact, top gate, bottom contact, bottom gate, or else a vertical construction, for example a VOFET (vertical organic field-effect transistor), as described, for example, in US 2004/0046182.

The layer thicknesses are, for example, from 10 nm to 5 μm in semiconductors, from 50 nm to 10 μm in the dielectric; the electrodes may, for example, be from 20 nm to 1 μm thick. The OFETs may also be combined to form other components such as ring oscillators or inverters.

A further aspect of the invention is the provision of electronic components which comprise a plurality of semiconductor components, which may be n- and/or p-semiconductors. Examples of such components are field-effect transistors (FETs), bipolar junction transistors (BJTs), tunnel diodes, converters, light-emitting components, biological and chemical detectors or sensors, temperature-dependent detectors, photodetectors such as polarization-sensitive photodetectors, gates, AND, NAND, NOT, OR, TOR and NOR gates, inverters, registers, switches, timer units, static or dynamic stores and other dynamic or sequential, logical or other digital components including programmable circuits.

The invention will now be described in more detail on the basis of the accompanying figure and the following examples. EXAMPLES

Examples 1 to 7

Tetrachloro diperylene bisimides (II) were prepared as disclosed by H. Quian, Z. Wang, W. Yue and D. Zhu in J. Am. Chem. Soc. 2007, 129, pages 10664-10665:

(II)

examples 1 - 4: R^a = R^b = 2,6-diisopropylphenyl examples 5 - 7: R^a = R^b = n-dodecyl

An aniline derivative I (x mg, 4 mmol) according to table 1 was added to a mixture of a tetrachlorodiperylene bisimide (II) (y mg, 1 mmol, see table 1 ), Pd(OAc)2 (88.9 mg, 0.4 mmol), PCy₃ (224 mg, 0.8 mmol), and KOf-Bu (894 mg, 8.0 mmol) in 2 ml toluene under Ar. The mixture was refluxed for 4 hours, and then cooled. After removal of the solvent under reduced pressure, the crude product was washed with HCI and extracted with CH2CI2. The organic layers were separated, washed with brine, dried over

Na2SU4, and purified by column separation on silica gel using CH2CI2 as eluent. The products (III) were obtained as green solids.

Table 1

Analytical Data of example 1 :

¹H NMR (CD₂CI₂, 300 MHz, 298K): δ = 10.93 (s, 2H), 9.80 (s, 2H,), 9.51 (s, 2H), 8.19(d, 4H), 7.86 (t, 4H), 7.67(t, 2H), 7.51 (t, 2H), 7.38 (m, 8H), 3.17 (m, 4H), 2.86 (m, 4H), 1.31 (d, 12H), 1.14 (d, 12H), 1.08 (m, 24H). ¹³C NMR (CD₂CI₂, 100 MHz, 298K): δ = 165.9, 165.6, 165.5, 164.6, 146.5, 146.4, 138.1 , 132.3, 131.1 , 130.2, 128.5, 125.9, 125.6, 125.4, 124.9, 124.3, 123.8, 123.2, 121.5, 121.3, 120.4, 1 19.4, 29.7, 29.3, 22.8. MS (MALDI-TOF): calcd for M-, 1592.6; found, 1592.4. Analytical Data of example 2:

¹H NMR (CDCI₃, 400 MHz, 298K): δ = 10.89 (s, 2H), 9.69 (s, 2H,), 9.42 (s, 2H), 8.00 (d, 4H), 7.46 (m, 4H), 7.34 (m, 12H), 3.97 (s, 6H), 3.10 (m, 4H), 2.80 (m, 4H), 1.29 (d, 12H), 1.19 (m, 12H), 1.09(m, 24H). ¹³C NMR (CDCI₃, 150 MHz, 298K): δ = 165.6, 165.2, 163.6, 160.1 , 146.1 , 138.6, 137.6, 132.6, 132.1 , 131.8, 130.6, 130.4, 126.9, 126.0, 125.0, 124.3, 124.1 , 123.9, 123.5, 122.8, 121.9, 121.3, 120.0, 1 16.2, 56.0, 29.8, 29.3, 24.7, 24.2, 22.8. MS (MALDI-TOF): calcd for M", 1652.7; found, 1652.1.

Analytical Data of example 3:

¹H NMR (CDCI₃, 400 MHz, 298K): δ = 10.98 (s, 2H), 9.85 (s, 2H,), 9.58 (s, 2H), 8.60 (d, 4H), 8.33 (m, 4H), 7.55 (t, 4H), 7.41 (m, 8H), 4.54 (q, 4H), 3.17 (m, 4H), 2.90 (m, 4H), 1.50 (t, 6H), 1.36 (d, 12H), 1.28 (m, 12H), 1.18 (m, 24H). MS (MALDI-TOF): calcd for M-, 1738.0; found, 1737.2.

Example 8: Synthesis of dichloro diperylene bisimide (C)

A reaction mixture of tetrachloro perylene bisimide (500 mg, 0.59 mmol), CuI (672 mg, 3.53 mmol), L-proline (475mg, 4.13 mmol), K₂CO₃ (814 mg, 5.9 mmol) in 10 ml DMSO was heated to 75°C under Ar atmosphere for 1 O h. The mixture was cooled, neutralized with 1 M HCI, and extracted with ethyl acetate. The organic layers were separated, washed with brine, dried over MgSO₄, and purified by column separation (silica gel, petroleum ether/C^Cb = 1 :1 ) to yield (C) as a purple black solid (43.7 mg, 10%).

Exampe 9: Synthesis of compound (28)

(28)

A mixture of Pd(OAc)₂ (44.9 mg, 0.20 mmol), PCy₃ (56.0 mg, 0.20 mmol), KO¹Bu (1 12 mg, 1.00 mmol), dichloro diperylene bisimide (C) from example 8 (192.8 mg, 0.13 mmol), and 4-amino-trisphenyl-porphyrin (94.4 mg, 0.15 mmol) in dry toluene (10.0 ml.) was stirred for 5 h at 1 10⁰C under Ar atmosphere. Ethyl acetate (50 ml.) and H₂O (50 ml.) were added to the reaction mixture at ambient temperature. The separated aqueous phase was extracted with ethyl acetate (3x30 ml_). The combined organic layers were washed with brine (50 ml_), dried over MgSO₄, and concentrated in vacuo. The remaining residue was purified by column chromatography on silica gel (petroleum ether/CH₂CI₂, 2:1 ) to yield (28) as a green solid (173.0 mg, 62.0%).

Example 10: Synthesis of compound (22)

(22)

A mixture of Pd(OAc)₂ (22.4 mg, 0.10 mmol), PCy₃ (28.0 mg, 0.10 mmol), KO¹Bu (560 mg, 5.00 mmol), dichloro diperylene bisimide (C) from example 8 (741.3 mg, 0.50 mmol) and 4-aminotriphenylamine (143 mg, 0.55 mmol) in dry toluence (50.0 ml.) was stirred for 5 h at 110⁰C under Ar atmosphere. Ethyl acetate (100 ml.) and H₂O (100 ml.) were added to the reaction mixture at ambient temperature. The separated aqueous phase was extracted with ethyl acetate (3x50 ml_). The combined organic layers were washed with brine (100 ml_), dried over MgSO₄, and concentrated in vacuo. The remaining residue was purified by column chromatography on silica gel (petroleum ether/CH₂CI₂, 2:1 ) to yield (22) as a green solid (530 mg, 63.4%).

Example 11 : Synthesis of compound (31 )

(31 )

A mixture of Pd(OAc)₂ (22.4 mg, 0.10 mmol), PCy₃ (28.0 mg, 0.10 mmol), KO¹Bu (560 mg, 5.00 mmol), dichloro diperylene bisimide (C) from example 8 (370.7 mg, 0.25 mmol) and 2,7-diamino-9,9-di(n-hexyl)fluorene (36.5 mg, 0.10 mmol) in dry toluence (30.0 ml.) was stirred for 5 h at 110⁰C under Ar atmosphere. Ethyl acetate (50 ml.) and H₂O (50 ml.) were added to the reaction mixture at ambient temperature. The separated aqueous phase was extracted with ethyl acetate (3x50 ml_). The combined organic layers were washed with brine (100 ml_), dried over MgSO₄, and concentrated in vacuo. The remaining residue was purified by column chromatography on silica gel (petroleum ether/ChbCb, 2:1 ) to yield (31 ) as a green solid (176 mg, 55.2%).

183/

Claims

What is claimed is:

1. Oligocondensed perylene bisimides, comprising two outer moieties of the formula Ia

and n inner moieties selected from moieties of the formulae (Ic) and (Id)

where

n is an integer from 0 to 6,

R¹ is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl or polycyclyl, or

2. Oligocondensed perylene bisimides according to claim 1 , wherein in the formulae

Ia, Ib, Ic and Id, R^a and R^b are each independently selected from groups of the formulae 11.1 to II.5:

(11-1 ) (II.2)

(II-3) (II.4)

# (A)_p — C(R^k)_y

(II.5)

where

# represents the bonding site to the imide nitrogen atom,

p is O or i ,

the R¹ radicals are each independently selected from Ci-C3o-alkyl, C1-C30- alkyloxy, Ci-C3o-alkylthio, fluorine, chlorine, bromine, NE¹E², nitro and cyano, where E¹ and E², independently of one another, are hydrogen, Ci-C3o-alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,

the R^k radicals are each independently selected from C4-C3o-alkyl, C4-C30- alkyloxy or C4-C3o-alkylthio, wherein the alkyl groups may be interrupted by one or more nonadjacent oxygen atom(s).

3. Oligocondensed perylene bisimides according to claim 2, wherein in the formulae

Ia, Ib, Ic and Id, R^a and R^b are each independently selected from groups of the formula 11.5 wherein the R^k radicals are each independently selected from linear C4-C3o-alkyl which may be interrupted by one or more nonadjacent oxygen atom(s).

4. Oligocondensed perylene bisimides according to any of claim 1 to 3, wherein all radicals R^a and R^b have the same meaning.

5. Oligocondensed perylene bisimides according to any of the preceding claims, where R¹ is a group of the formula III

where

R⁴ is hydrogen or an organyl group, and

6. Oligocondensed perylene bisimides according to claim 5, wherein the residue R⁴ is selected from hydrogen, Ci-Ci₂-alkyl, Ci-Ci₂-alkoxy, COOH, COO(Ci-C₄-alkyl), aryl or polycyclyl.

7. Oligocondensed perylene bisimides according to claim 5 or 6, where R¹ is a group of the formula 111.1

(111.1 ) where

8. Oligocondensed perylene bisimides according to claim 5 or 6, where R¹ is a group of the formula 111.2

(III.2)

where

^* represents the attachment site to the nitrogen atom of the perylene skeleton,

9. Oligocondensed perylene bisimides according to any of claims 1 to 4, where two substituents R¹ form a divalent bridging group X between two moieties of the formula Ia, wherein X has from 1 to 20 bridge atoms between the flanking bonds.

10. Oligocondensed perylene bisimides according to claim 9, wherein the bridging group X is a group of the formula

1 1. Oligocondensed perylene bisimides according to any of the preceding claims, where R² and R³ are selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl or halogen.

12. Oligocondensed perylene bisimides according to any of the preceding claims, comprising one outer moiety of the formula Ia and one outer moiety of the formula

Ib, wherein R² and R³ are both hydrogen or R² and R³ are both chlorine.

13. A process for preparing oligocondensed perylene bisimides, comprising

- two outer moieties of the formula Ia

(Ia)

or one outer moiety of the formula Ia and one outer moiety of the formula Ib

and

n inner moieties selected from moieties of the formulae (Ic) and (Id)

where

#, R^a, R^b, n, R² and R³ are defined as in any of claims 1 to 5 or 8 and

wherein oligocondensed perylene bisimides, comprising

two outer moieties of the formula IVa

(IVa)

or one outer moiety of the formula IVa and one outer moiety of the formula Ib

14. A process for preparing oligocondensed perylene bisimides, comprising

two outer moieties of the formula Ia

and n inner moieties selected from moieties of the formulae (Ic) and (Id)

where #, R^a, R^b, n, R² and R³ are defined as in any of claims 1 to 5 or 8 and

wherein oligocondensed perylene bisimides, comprising

two outer moieties of the formula IVa

(IVa)

or one outer moiety of the formula IVa and one outer moiety of the formula Ib

15. A composition of oligocondensed perylene bisimides, obtainable by a process as defined in any of claims 13 or 14.

16. An organic field-effect transistor comprising a substrate having at least one gate structure, a source electrode and a drain electrode and at least one oligocondensed perylene bisimide as defined in any of claims 1 to 12 or obtained by a process as defined in any of claims 13 or 14 as a semiconductor.

17. A substrate having a multitude of organic field-effect transistors, at least some of the field-effect transistors comprising at least one oligocondensed perylene bisimide as defined in any of claims 1 to 12 or obtained by a process as defined in any of claims 13 or 14 as a semiconductor.

18. A semiconductor component comprising at least one substrate as defined in claim 17.

19. The use of oligocondensed perylene bisimide as defined in any of claims 1 to 12 or obtained by a process as defined in any of claims 13 or 14 in organic electronics, especially in organic field-effect transistors, organic light-emitting diodes or in solar cells.

20. The use of oligocondensed perylene bisimide as defined in any of claims 1 to 12 or obtained by a process as defined in any of claims 13 or 14 for optical labels, for invisible marking of products and as pigments.

21. The use of oligocondensed perylene bisimide as defined in any of claims 1 to 12 or obtained by a process as defined in any of claims 13 or 14 in a light-collecting plastics component which is, if appropriate, combined with a solar cell; as a pigment dye in electrophoretic displays.

22. The use of oligocondensed perylene bisimide as defined in any of claims 1 to 12 or obtained by a process as defined in any of claims 13 or 14 for coloring organic and inorganic materials.

23. The use of oligocondensed perylene bisimide as defined in any of claims 1 to 12 or obtained by a process as defined in any of claims 13 or 14 for obtaining markings and inscriptions which absorb infrared light but are invisible to the human eye.

24. The use of oligocondensed perylene bisimide as defined in any of claims 1 to 12 or obtained by a process as defined in any of claims 13 or 14 as infrared absorbers for heat management.