Description

Organic semiconducting materials can be used in electronic devices such as organic photovol- taic (OPV) cells, organic field-effect transistors (OFETs) and organic light emitting diodes (OLEDs).

For efficient and long lasting performance, it is desirable that the organic semiconducting material-based devices show high charge carrier mobility and high stability, in particular towards oxi- dation, under ambient conditions.

Furthermore, it is desirable that the organic semiconducting materials are compatible with liquid processing techniques as liquid processing techniques are convenient from the point of pro- cessability, and thus allow the production of low cost organic semiconducting material-based electronic devices. In addition, liquid processing techniques are also compatible with plastic substrates, and thus allow the production of light weight and flexible organic semiconducting material-based electronic devices.

Perylene bisimide-based organic semiconducting materials suitable for use in electronic devices are known in the art.

R. Schmidt, J. H. Oh, Y.-S. Sun, M. Deppisch, A.-M. Krause, K. Radacki, H. Braunschweig, M. Konemann, P. Erk, Z. Bao and F. Wurthner J. Am. Chem. Soc. 2009, 131, 6215-6228 describes halogenated perylene bisimide derivatives, for example

S. Nakazono, Y. Imazaki, H. Yoo, J. Yang, T. Sasamori, N. Tokitoh, T. Cedric, H. Kageyama, D. Kim, H. Shinokubo and A. Osuka Chem. Eur. J. 2009, 15, 7530-7533 describes the preparation of 2,5,8,1 1 tetraalkylated perylene tetracarboxylic acid bisimides from perylene tetracarboxylic acid bisimides

S. Nakanzono, S. Easwaramoorthi, D. Kim, H. Shinokubo, A. Osuka Org. Lett. 2009, 11, 5426 to 5429 describes the preparation of 2,5,8,1 1 tetraarylated perylene tetracarboxylic acid bisimides from perylene tetracarboxylic acid bisimides

US 7,355,198 B2 describes an organic thin film transistor (OFET), which interposes an organic acceptor film between source and drain electrodes and an organic semiconductor film. The organic semiconductor film is formed of pentacene. In particular, the organic acceptor film is formed of at least one electron withdrawing material selected from a long list of compounds, including N,N'-bis(di-ferf-butyphenyl)-3,4,9,10-perylenedicarboximide.

US 7,326,956 B2 describes a thin film transitor comprising a layer of organic semiconductor material comprising tetracarboxylic diimide perylene-based compound having attached to each of the imide nitrogen atoms a carbocyclic or heterocyclic aromatic ring system substituted with one or more fluorine containing groups. In one embodiment the fluorine-containing N,N'-diaryl perylene-based tetracarboxylic diimide compound is represented by the following structure:

wherein A ¹ and A ² are independently carbocyclic and/or heterocyclic aromatic ring systems comprising at least one aromatic ring in which one or more hydrogen atoms are substituted with at least one fluorine-containing group. The perylene nucleus can be optionally substituted with up to eight independently selected X groups, wherein n is an integer from 0 to 8. The X substit- uent groups on the perylene can include a long list of substituents, including halogens such as fluorine or chlorine.

WO 2007/093643 describes fluorinated rylenetetracarboxylic acid derivatives. Preferred pounds are of formula IBa

wherein 1 , 2, 3, 4, 5 or 6 of the residues R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ are F, optionally at least one of the residues R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ , which is not F, can independently be CI or Br, and the remaining residues are H, and

R ^a and R ^b are independently from each other are H or an organic residue. WO 2008/063609 describes a compound having the following formula 1

wherein A, B, I, D, E, F, G and H are independently selected from a group of substituents, in- eluding, CH and CR ^a , wherein R ^a can be selected from a list of substituents, including halogen. For example, A, B, I, D, E, F, G and H can be independently CH, C-Br or C-CN.

WO 2009/024512 describes halogen-containing perylenetetracarboxylic acid derivatives, and in particular compound IBa

wherein the residues R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ are CI and/or F, wherein 1 or 2 of the residues R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ can be CN, and/or , and wherein 1 of the residues R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ can be H, and

R ^a and R ^b are independently from each other are H or an organic residue.

G. Battagliari; C. Li, V. Enkelmann, K. Mullen Org. Lett. 2011 , 13, 3012-3015 describe compounds of formula

G. Battagliari; Y. Zhao; C. Li, K. Mullen Org. Lett. 2011 , 13, 3399-3401 describe compounds of formulae

So far, it has not been possible to prepare 2,5,8,1 l-tetrafluoroperylene-bis(dicarboximides).

It was the object of the present invention to provide 2,5,8,11 -tetrafluoroperylene- bis(dicarboximides). The object is solved by the compound of claim 1 , the process of claim 5, and the electronic d vice of claim 6.

The perylene-based semiconducting compound of the present invention is of formula

wherein

R ¹ and R ² are independently from each other selected from the group consisting of H, Ci-30-alkyl optionally substituted with 1 to 30 substituents R ^a , C2-3o-alkenyl optionally substituted with 1 to 30 substituents R ^a , C2-3o-alkynyl optionally substituted with 1 to 30 substituents R ^a , C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R ^b , Cs-io-cycloalkenyl option- ally substituted with 1 to 10 substituents R , 3-14 membered cycloheteroalkyl optionally substituted with 1 to 8 substituents R ^b , C6-i4-aryl optionally substituted with 1 to 8 substituents R ^c and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R ^c , wherein

R ^a at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -N ₃ , -OH, Ci-30-alkoxy optionally substituted with 1 to 6 substituents R ⁱ -0-[CH ₂ CH ₂ 0]n-Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10),

-O-COR ³ , -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R, -S0 ₂ -Ci- ₃ o-alkyl optionally substituted with 1 to 30 substituents R', -NH ₂ , -NHR ³ , -NR ³ R ⁴ , -[NR ³ R ⁴ R ⁵ ] ⁺ ,

-NH-COR ³ , -COOH, -COOR ³ , -CON H2, -CONHR ³ , -CONR ³ R ⁴ , -CO-H, -COR ³ , C ₃ -io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyl optionally substituted with 1 to 10 substituents R", C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R ^Hi ;

R at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -OH, Ci-30-alkoxy optionally substituted with 1 to 30 substituents R ⁱ , -0-[CH ₂ CH ₂ 0] _n -Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ³ , -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R\ -NH ₂ , -NH ³ , -NR ³ R ⁴ , -[NR ³ R ⁴ R ⁵ ] ⁺ , -NH-COR ³ , -COOH, -COOR ³ , -CONH ₂ , -CONHR ³ , -CONR ³ R ⁴ , -CO-H, -COR ³ , Ci-30-alkyl optionally substituted with 1 to 30 substituents R\ C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C ₂ -3o-alkynyl optionally substituted with 1 to 30 substitu- ents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", C ₅ -io-cycloalkenyl optionally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R'',C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R ^iN ;

R ^c at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -N ₃ , -OH, Ci-30-alkoxy optionally substituted with 1 to 30 substituents R, -0-[CH ₂ CH ₂ 0]n-Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ³ , -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R, -S0 ₂ -Ci- ₃ o-alkyl optionally substituted with 1 to 30 substituents R -NH ₂ , -NHR ³ , -NR ³ R ⁴ , -[NR ³ R ⁴ R ⁵ ] ⁺ ,

-NH-COR ³ , -COOH, -COOR ³ , -CONH ₂ , -CONHR ³ , -CONR ³ R ⁴ , -CO-H, -COR ³ , Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C _2- 3o-alkenyl optionally substituted with 1 to 30 substituents R', C ₂ -3o-alkynyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", C ₅ -io-cycloalkenyl option- ally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R", C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R'"; wherein

R ³ , R ⁴ and R ⁵ at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C ₂ -3o-alkenyl optionally substituted with 1 to 30 substituents R', C _2- 3o-alkynyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R", C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R'",

R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -N ₃ , -OH, Ci-30-alkoxy, -O-[CH ₂ CH ₂ O] _n -Ci-i ₀ -alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ³ , -S-Ci-30-alkyl, -SO ₂ -Ci- ₃₀ -alkyl, -NH ₂ , -NHR ⁶ , -NR ⁶ R ⁷ , -[NR ⁶ R ⁷ R ⁸ ] ⁺ , -NH-COR ⁵ , -COOH, -COOR ⁶ , -CONH ₂ , -CONHR ⁶ , -CONR ⁶ R ⁷ , -CO-H, -COR ⁶ , C ₃ -io-cycloalkyl, C ₅ -io-cycloalkenyl, 3-14 membered cycloheteroalkyi, C6-i4-aryl and 5-14 membered heteroaryl,

R" at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N0 ₂ , -OH, Ci-30-alkoxy, -O-[CH ₂ CH ₂ O] _n -Ci-i ₀ -alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-CO ⁶ , -S-Ci _-3 o-alkyl, -NH ₂ , -NH ⁵ , -NR ⁶ R ⁷ , -[NR ⁶ R ⁷ R ⁸ ] ⁺ , -NH-COR ⁶ , -COOH, -COOR ⁶ , -CONH ₂ , -CONHR ⁶ , -CONR ⁶ R ⁷ , - CO-H, -COR ⁶ , Ci-3o-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, C5-10- cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered het- eroaryl,

R ^iN at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -N ₃ , -OH, Ci- ₃₀ -alkoxy, -0-[CH ₂ CH ₂ 0]n-Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ⁶ , -S-Ci-30-alkyl, -S0 ₂ -Ci _-3 o-alkyl, -NH ₂ , -NHR ⁶ , -NR ⁶ R ⁷ , -[NR ⁶ R ⁷ R ⁸ ] ⁺ , -NH-COR ⁵ , -COOH, -COOR ⁶ , -CONH ₂ , -CONHR ⁶ ,

-CONR ⁶ R ⁷ , -CO-H, -COR ⁶ , Ci-30-alkyl, C ₂ . ₃ o-alkenyl, C _2-3 o-alkynyl, C _3- io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl, wherein

R ^s , R ⁷ and R ⁸ at each occurrence are independently from each other selected from the group consisting of Ci _-3 o-alkyl, C ₂ -3o-alkenyl, C _2-3 o-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl , C6-i4-aryl and 5-14 membered heteroaryl.

Ci-10-alkyl and Ci-30-alkyl can be branched or unbranched. Examples of Ci-10-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl and n-decyl. Examples of C3-8-alkyl are n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-butyl, n-pentyl , neopentyl, isopentyl, n-(1-ethyl)propyl, n-hexyl, n-heptyl, n-octyl and n-(2-ethyl)hexyl. Examples of Ci-30-alkyl are Ci-10-alkyl, and n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C ₂ o), n-docosyl (C ₂₂ ), n-tetracosyl (C ₂ 4), n-hexacosyl (C ₂ s), n-octacosyl (C ₂ e) and n-triacontyl (C30). Examples of C3- ₂ 5-alkyl branched at the C attached to the N of formula I are isopropyl, sec-butyl, n-(1-methyl)propyl, n-(1 - ethyl)propyl, n-(1-methyl)butyl, n-(1 -ethyl)butyl, n-(1 -propyl) butyl, n-(1-methyl)pentyl, n-(1 - ethyl)pentyl, n-(1 -propyl)pentyl, n-(1-butyl)pentyl, n-(1 -butyl)hexyl, n-(1-pentyl)hexyl, n-(1- hexyl)heptyl, n-(1-heptyl)octyl, n-(1-octyl)nonyl, n-(1-nonyl)decyl, n-(1 -decyl)undecyl, n-(1- undecyl)dodecyl and n-(1 -dodecyl)tridecyl.

C ₂ -3o-alkenyl can be branched or unbranched. Examples of C ₂ -3o-alkenyl are vinyl, propenyl, cis-

2- butenyl, frans-2-butenyl, 3-butenyl, c/s-2-pentenyl, frans-2-pentenyl, c/s-3-pentenyl, trans-

3- pentenyl , 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl, linoleyl (Cie), linolenyl (Cie), oleyl (Cie), arachidonyl (C ₂ o), and erucyl (C ₂₂ ).

C ₂ - ₃ o-alkynyl can be branched or unbranched. Examples of C ₂ - ₃ o-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl , octynyl , nonynyl and decynyl, undecynyl , do- g

decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptade- cynyl, octadecynyl, nonadecynyl and icosynyl (C20).

Examples of C3-io-cycloalkyl are preferably monocyclic C3-io-cycloalkyls such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, but include also polycyclic

C3-io-cycloalkyls such as decalinyl, norbornyl and adamantyl.

Examples of Cs-io-cycloalkenyl are preferably monocyclic Cs-io-cycloalkenyls such as cyclopen- tenyl, cyclohexenyl, cyclohexadienyl and cycloheptatrienyl, but include also polycyclic

C ₅ -io-cycloalkenyls.

Examples of 3-14 membered cycloheteroalkyi are monocyclic 3-8 membered cycloheteroalkyi and polycyclic, for example bicyclic 7-12 membered cycloheteroalkyi. Examples of monocyclic 3-8 membered cycloheteroalkyi are monocyclic 5 membered cycloheteroalkyi containing one heteroatom such as pyrrolidinyl, 1-pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydrofuryl, 2,3-dihydrofuryl, tetrahydrothiophenyl and 2,3-dihydrothiophenyl, monocyclic

5 membered cycloheteroalkyi containing two heteroatoms such as imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, oxazolidinyl, oxazolinyl, isoxazolidinyl, isoxazolinyl, thiazolidinyl, thia- zolinyl, isothiazolidinyl and isothiazolinyl, monocyclic 5 membered cycloheteroalkyi containing three heteroatoms such as 1 ,2,3-triazolyl, 1 ,2,4-triazolyl and 1 ,4,2-dithiazolyl, monocyclic

6 membered cycloheteroalkyi containing one heteroatom such as piperidyl, piperidino, tetrahy- dropyranyl, pyranyl, thianyl and thiopyranyl, monocyclic 6 membered cycloheteroalkyi containing two heteroatoms such as piperazinyl, morpholinyl and morpholino and thiazinyl, monocyclic 7 membered cycloheteroalkyi containing one hereoatom such as azepanyl, azepinyl, oxepanyl, thiepanyl, thiapanyl, thiepinyl, and monocyclic 7 membered cycloheteroalkyi containing two hereoatom such as 1 ,2-diazepinyl and 1 ,3-thiazepinyl.

An example of a bicyclic 7-12 membered cycloheteroalkyi is decahydronaphthyl.

C6-i4-aryl can be monocyclic or polycyclic. Examples of C6-i4-aryl are monocyclic C6-aryl such as phenyl, bicyclic C9-io-aryl such as 1-naphthyl, 2-naphthyl, indenyl, indanyl and tetrahydronaph- thyl, and tricyclic Ci2-i4-aryl such as anthryl, phenanthryl, fluorenyl and s-indacenyl.

5-14 membered heteroaryl can be monocyclic 5-8 membered heteroaryl, or polycyclic 7-14 membered heteroaryl, for example bicyclic 7-12 membered or tricyclic 9-14 membered heteroaryl. Examples of monocyclic 5-8 membered heteroaryl are monocyclic 5 membered heteroaryl containing one heteroatom such as pyrrolyl, furyl and thiophenyl, monocyclic 5 membered heteroaryl containing two heteroatoms such as imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, monocyclic 5 membered heteroaryl containing three heteroatoms such as

1 ,2,3-triazolyl, 1 ,2,4-triazolyl and oxadiazolyl, monocyclic 5 membered heteroaryl containing four heteroatoms such as tetrazolyl, monocyclic 6 membered heteroaryl containing one heteroa- tom such as pyridyl, monocyclic 6 membered heteroaryl containing two heteroatoms such as pyrazinyl, pyrimidinyl and pyridazinyl, monocyclic 6 membered heteroaryl containing three heteroatoms such as 1 ,2,3-triazinyl, 1 ,2,4-triazinyl and 1 ,3,5-triazinyl, monocyclic / membered heteroaryl containing one heteroatom such as azepinyl, and monocyclic 7 membered heteroaryl containing two heteroatoms such as 1 ,2-diazepinyl. Examples of bicyclic 7-12 membered heteroaryl are bicyclic 9 membered heteroaryl containing one heteroatom such as indolyl, isoindolyl, indolizinyl, indolinyl, benzofuryl, isobenzofuryl, ben- zothiophenyl and isobenzothiophenyl, bicyclic 9 membered heteroaryl containing two heteroatoms such as indazolyl, benzimidazolyl, benzimidazolinyl, benzoxazolyl, benzisooxazolyl, benzthiazolyl, benzisothiazolyl, furopyridyl and thienopyridyl, bicyclic 9 membered heteroaryl containing three heteroatoms such as benzotriazolyl, benzoxadiazolyl, oxazolopyridyl, isooxa- zolopyridyl, thiazolopyridyl, isothiazolopyridyl and imidazopyridyl, bicyclic 9 membered heteroaryl containing four heteroatoms such as purinyl, bicyclic 10 membered heteroaryl containing one heteroatom such as quinolyl, isoquinolyl, chromenyl and chromanyl, bicyclic 10 membered heteroaryl containing two heteroatoms such as quinoxalinyl, quinazolinyl, cinnolinyl, phthalazi- nyl, 1 ,5-naphthyridinyl and 1 ,8-naphthyridinyl, bicyclic 10 membered heteroaryl containing three heteroatoms such as pyridopyrazinyl, pyridopyrimidinyl and pyridopyridazinyl, and bicyclic 10 membered heteroaryl containing four heteroatoms such as pteridinyl.

Examples of tricyclic 9-14 membered heteroaryls are dibenzofuryl, acridinyl, phenoxazinyl, 7H- cyclopenta[1 ,2-b:3,4-b']dithiophenyl and 4H-cyclopenta[2,1-b:3,4-b']dithiophenyl.

Examples of halogen are -F, -CI, -Br and -I .

Examples of Ci-30-alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, ferf-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, n-tridecoxy, n-tetradecoxy, n-pentadecoxy, n-hexadecoxy, n-heptadecoxy, n-octadecoxy and n-nonadecoxy. Examples of C2-5-alkylene are ethylene, propylene, butylene and pentylene. Preferably,

R ¹ and R ² are independently from each other selected from the group consisting of H , Ci-30-alkyl optionally substituted with 1 to 30 substituents R ^a , C2-3o-alkenyl optionally substituted with 1 to 30 substituents R ^a , C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R ^b , and C6-i4-aryl optionally substituted with 1 to 8 substituents R ^c , wherein

R ^a at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -N ₃ , -OH, O-30-alkoxy optionally substituted with 1 to 6 substitu- ents R ⁱ -0-[CH ₂ CH ₂ 0]n-Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10),

-O-COR ³ , -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R, -S0 ₂ -Ci- ₃ o-alkyl optionally substituted with 1 to 30 substituents R', -NH ₂ , -NHR ³ , -NR ³ R ⁴ , -[NR ³ R ⁴ R ⁵ ] ⁺ , -NH-COR ³ , -COOH, -COOR ³ , -CONH2, -CONHR ³ , -CONR ³ R ⁴ , -CO-H, -COR ³ , C ₃ -io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R ^Hi ;

R at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -OH, Ci-30-alkoxy optionally substituted with 1 to 30 substituents R ⁱ , -0-[CH ₂ CH ₂ 0] _n -Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ³ , -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R\ -NH ₂ , -NHR ³ , -NR ³ R ⁴ ,

-[NR ³ R ⁴ R ⁵ ] ⁺ , -NH-COR ³ , -COOH, -COOR ³ , -CONH ₂ , -CONHR ³ , -CONR ³ R ⁴ , -CO-H, -COR ³ , Ci-3o-alkyl optionally substituted with 1 to 30 substituents R\ C _2- 3o-alkenyl optionally substituted with 1 to 30 substituents R', C ₃ -io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R"';

R ^c at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N0 ₂ , -N ₃ , -OH, Ci-30-alkoxy optionally substituted with 1 to 30 substituents R, -0-[CH ₂ CH ₂ 0] _n -Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ³ , -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R, -S0 ₂ -Ci- ₃ o-alkyl optionally substituted with 1 to 30 substituents R -NH ₂ , -NHR ³ , -NR ³ R ⁴ , -[NR ³ R ⁴ R ⁵ ] ⁺ ,

-NH-COR ³ , -COOH, -COOR ³ , -CONH ₂ , -CONHR ³ , -CONR ³ R ⁴ , -CO-H, -COR ³ , Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C _2- 3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R"'; wherein

R ³ , R ⁴ and R ⁵ at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C ₂ -3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl option- ally substituted with 1 to 10 substituents R", and Cs-i4-aryl optionally substituted with

1 to 8 substituents R'",

R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N0 ₂ , -N ₃ , -OH, Ci-30-alkoxy, -O-[CH ₂ CH ₂ O] _n -Ci-i ₀ -alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ³ , -S-C _1-3 o-alkyl, -SO ₂ -Ci- ₃₀ -alkyl,

-NH ₂ , -NHR ⁶ , -NR ⁶ R ⁷ , -[NR ⁶ R ⁷ R ⁸ ] ⁺ , -NH-COR ⁵ , -COOH, -COOR ⁶ , -CONH ₂ , -CONHR ⁶ , -CONR ⁶ R ⁷ , -CO-H, -COR ⁶ , C _3- io-cycloalkyl, and C ₆ -i ₄ -aryl, R" at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N0 ₂ , -OH, Ci- ₃₀ -alkoxy, -0-[CH ₂ CH ₂ 0]n-Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ⁶ , -S-Ci-ao-alkyl, -NH ₂ , -NHR ⁶ , -NR ⁶ R ⁷ , -[NR ⁶ R ⁷ R ⁸ ] ⁺ , -NH-COR ⁵ , -COOH, -COOR ⁶ , -CONH ₂ , -CONHR ⁶ , -CONR ⁶ R ⁷ , -

CO-H, -COR ⁶ , Ci-3o-alkyl, C ₂ -3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl,

R ^iN at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N0 ₂ , -N ₃ , -OH, Ci-30-alkoxy, -0-[CH ₂ CH ₂ 0] _n -Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ⁶ , -S-Ci-3o-alkyl, -SO ₂ -Ci- ₃₀ -alkyl,

-NH ₂ , -NHR ⁶ , -NR ⁶ R ⁷ , -[NR ⁶ R ⁷ R ⁸ ] ⁺ , -NH-COR ⁶ , -COOH, -COOR ⁶ , -CONH ₂ , -CONHR ⁶ , -CONR ⁶ R ⁷ , -CO-H, -COR ⁶ , Ci _-3 o-alkyl, C ₂ . ₃₀ -alkenyl, C _3- io-cycloalkyl, and Ce-n-aryl, wherein

R ^s , R ⁷ and R ⁸ at each occurrence are independently from each other selected from the group consisting of Ci _-3 o-alkyl, C ₂ . ₃ o-alkenyl, C ₃ -io-cycloalkyl, and C6-i4-aryl.

More preferably,

R ¹ and R ² are independently from each other Ci _-3 o-alkyl optionally substituted with 1 to 30 sub- stituents R ^a , wherein R ^a at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N0 ₂ , -N ₃ , -OH, Ci- ₃ o-alkoxy optionally substituted with 1 to 6 substitu- ents R ⁱ , -0-[CH ₂ CH ₂ 0]n-Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10),

-O-COR ³ , -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R\ -SO ₂ -Ci- ₃₀ -alkyl optionally substituted with 1 to 30 substituents R', -NH ₂ , -NHR ³ , -NR ³ R ⁴ , -[NR ³ R ⁴ R ⁵ ] ⁺ , -NH-COR ³ , -COOH, -COOR ³ , -CONH ₂ , -CONHR ³ , -CONR ³ R ⁴ , -CO-H, -COR ³ , C ₃ -io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R'"; wherein

R ³ , R ⁴ and R ⁵ at each occurrence are independently from each other selected from the group consisting of Ci- ₃ o-alkyl optionally substituted with 1 to 30 substituents R', C ₂ . ₃ o-alkenyl optionally substituted with 1 to 30 substituents R', C _3- io-cycloalkyl optionally substituted with 1 to 10 substituents R'\ and C6-i4-aryl optionally substituted with 1 to 8 substituents R ^iH ,

R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N0 ₂ , -N ₃ , -OH, Ci _-30 -alkoxy, -O-[CH ₂ CH ₂ O] _n -Ci-i ₀ -alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -OH (m = 1 to 10), -O-COR ³ , -S-Ci _-3 o-alkyl, -NH ₂ , -NHR ⁵ , -S0 ₂ -Ci-3o-alkyl, -NR ⁶ R ⁷ , -[NR ⁶ R ⁷ R ⁸ ] ⁺ , -NH-COR ⁶ , -COOH, -COOR ⁶ , -CONH ₂ , -CONHR ⁶ , -CONR ⁶ R ⁷ , -CO-H, -COR ⁶ , C ₃ -io-cycloalkyl, and C ₆ -i ₄ -aryl, R" at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N0 ₂ , -OH, Ci- ₃ o-alkoxy, -0-[CH ₂ CH ₂ 0] _n -Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0] _m -0H (m = 1 to 10), -O-COR ⁶ , -S-Ci _-3 o-alkyl, -NH ₂ , -NHR ⁶ , -NR ⁶ R ⁷ , -[NR ⁶ R ⁷ R ⁸ ] ⁺ , -NH-COR ⁶ , -COOH, -COOR ⁶ , -CONH ₂ , -CONHR ⁶ , -CONR ⁶ R ⁷ , - CO-H, -COR ⁶ , Ci-3o-alkyl, C ₂ -3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl,

R ^iN at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N0 ₂ , -N ₃ , -OH, Ci-30-alkoxy, -0-[CH ₂ CH ₂ 0] _n -Ci-io-alkyl (n = 1 to 10), -0-[CH ₂ CH ₂ 0]m-OH (m = 1 to 10), -O-COR ⁶ , -S-Ci _-30 -alkyl, -SO ₂ -Ci- ₃₀ -alkyl, -NH ₂ , -NHR ⁶ , -NR ⁶ R ⁷ , -[NR ⁶ R ⁷ R ⁸ ] ⁺ , -NH-COR ⁶ , -COOH, -COOR ⁶ , -CONH ₂ , -CONHR ⁶ , -CONR ⁶ R ⁷ , -CO-H, -COR ⁶ , Ci- ₃₀ -alkyl, C ₂ . ₃₀ -alkenyl, C ₃ -io-cycloalkyl, and Ce-n-aryl, wherein

R ⁶ , R ⁷ and R ⁸ at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C ₂ -3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl.

Most preferably,

R ¹ and R ² are independently from each other C3- ₂ 5-alkyl branched at the C attached to the N of formula 1. Particular preferred is the compound of formula

Also part of the invention, is a process for the preparation of the compound of formula 1

wherein R ¹ and R ² are as defined above, which process comprises the steps of

(i) treating a compound of formula (5)

wherein R ¹ and R ² are as defined above, and X is CI, Br or I, with a fluoride source.

The fluoride source can be an alkali fluoride, such as potassium fluoride. Usually the ratio of molequivalents fluoride source/compound of formula (5) is in the range of 1/1 to 30/1 , preferably in the range of 10/1 to 30/1. The reaction is usually performed at temperatures between 100 °C and 200 °C, preferably between 130 °C to 180 °C. The reaction is usually performed in a sealed reaction vessel.

The reaction is usually performed in an aprotic solvent. Preferred aprotic solvents are ethers such as dioxane and diglyme (bis(2-methoxyethyl) ether) or mixtures thereof. X is preferably CI.

The compounds of formula (5) can be prepared as described by G. Battagliari; C. Li, V. Enkel- mann, K. Mullen Org. Lett. 2011 , 13, 3012-3015, and G. Battagliari; Y. Zhao; C. Li, K. Mullen Org. Lett. 2011 , 13, 3399-3401.

The compounds of formula (1 ) can be isolated by methods known in the art, such as column chromatography.

Also part of the present invention is an electronic device comprising the compound of formula (1 ) as semiconducting material. Preferably, the electronic device is an organic field effect transistor (OFET). Usually, an organic field effect transistor comprises a dielectric layer, a semiconducting layer and a substrate. In addition, an organic field effect transistor usually comprises a gate electrode and source/drain electrodes.

An organic field effect transistor can have various designs.

The most common design of an organic field-effect transistor is the bottom-gate design. Examples of bottom-gate designs are shown in Figures 1.

Another design of an organic field-effect transistor is the top-gate design. Examples of top-gate designs are shown in Figure 2.

The semiconducting layer comprises the semiconducting material of the present invention. The semiconducting layer can have a thickness of 5 to 500 nm, preferably of 10 to 100 nm, more preferably of 20 to 50 nm.

The dielectric layer comprises a dielectric material. The dielectric material can be silicon dioxide, or, an organic polymer such as polystyrene (PS), poly(methylmethacrylate) (PMMA), poly(4-vinylphenol) (PVP), polyvinyl alcohol) (PVA), benzocyclobutene (BCB), or polyimide (PI). The dielectric layer can have a thickness of 10 to 2000 nm, preferably of 50 to 1000 nm, more preferably of 100 to 800 nm.

The source/drain electrodes can be made from any suitable source/drain material, for example gold (Au) or tantalum (Ta). The source/drain electrodes can have a thickness of 1 to 100 nm, preferably from 5 to 50 nm. The gate electrode can be made from any suitable gate material such as highly doped silicon, aluminium (Al), tungsten (W), indium tin oxide, gold (Au) and/or tantalum (Ta). The gate electrode can have a thickness of 1 to 200 nm, preferably from 5 to 100 nm. The substrate can be any suitable substrate such as glass, or a plastic substrate such as poly- ethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Depending on the design of the organic field effect transistor, a combination of the gate electrode and the dielectric layer can also function as substrate. The organic field effect transistor can be prepared by methods known in the art.

For example, a bottom-gate organic field effect transistor can be prepared as follows:

The gate electrode can be formed by depositing the gate material, for example highly doped silicon, on one side of the dielectric layer made of a suitable dielectric material, for example si- licium dioxide. The other side of the dielectric layer can be optionally treated with a suitable reagent, for example with hexamethyldisilazane (HMDS). Source/drain electrodes can be deposited on this side (the side which is optionally treated with a suitable reagent) of the dielectric layer for example by vapour deposition of a suitable source/drain material, for example tantalum (Ta) and/or gold (Au). The source/drain electrodes can then be covered with the semiconducting layer by solution processing, for example drop coating, a solution of the semiconducting material of the present invention in s suitable solvent, for example in chloroform.

Also part of the invention is the use of the compound of formula (1 ) as semiconducting material.

In Figure 1 two designs of a bottom-gate organic field effect transistor are shown. In Figure 2 two designs of a top-gate organic field effect transistor are shown.

The advantage of the semiconducting materials of the present invention is the high solubility of these materials in solvents suitable for solution processing. In addition the semiconducting materials of the present invention show acceptable charge carrier mobility.

Examples

Example 1

Preparation of /V,/V'-bis(1-heptyloctyl)-2, 5,8,11-tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl]perylene-3,4:9,10-tetracarboxylic acid bisimide (4a)

/V,/V'-Bis(1-heptyloctyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2a) (100 mg, 0.12 mmol) and bispinacolonediboronate (3a) (250 mg, 0.99 mmol) are mixed together and dissolved in 1 mL anhydrous mesitylene and 1 mL anhydrous pinacolone. Argon is bubbled through the solution for 30 minutes. RuH2(CO)(PPh3)3 (23 mg, 0,03 mmol) is added to the mixture and the reaction mixture is heated at 140°C for 30 hours. After cooling the system to room temperature, the solvent is evaporated and the desired compound purified by column chromatography (CH2CI2). 4a is obtained as a red solid in 70% yield (113 mg, 0.09 mmol).

¹ H NMR (250 MHz, CD ₂ CI ₂ ) δ 8.58 (s, 4H), 5.06 (s, 2H), 2.35 - 2.06 (m, 4H), 1.98 - 1.72 (m, 4H), 1.50 (s, 48H), 1.24 (s, 40H), 0.84 (t, J = 6.5 Hz, 12H). ¹³ C NMR (126 MHz, CD2CI2) δ 166.27 (d, J = 98.5 Hz), 139.79 - 138.86 (m), 133.80 (s), 128.82 (s), 127.57 (d, J = 69.0 Hz), 127.30 (s), 126.29 (s), 84.90 (s), 55.19 (s), 32.83 (s), 32.45 (s), 30.03 (s), 29.76 (s), 27.37 (s), 25.38 (s), 23.22 (s), 14.43 (s). FD/MS (8kV): m/z= 1312.4 (100%) [M+]. UV-Vis(in toluene): Amax( [M- ¹ cm- ¹ ]): 538 nm (5,57 X 10 ⁴ ). Fluorescence (in toluene, A _ex = 538 nm): 548 nm. <D _F : 0.83. Elem. Anal.: theoretical: C: 71.24%; H : 8.74%; N: 2.13%; experimental: C: 70.76%; H: 8.27%; N: 2.50%.

/V,/V'-Bis(1-heptyloctyl)-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]perylene- 3,4:9,10-tetracarboxylic acid bisimide (4a), prepared as described in example 1 , (1.00 g, 0.76 mmol) and copper(ll) chloride (1 .23 g, 9.13 mmol) are suspended in a mixture of methanol (3 mL) and water (3 mL) and heated in a closed vessel at 100 °C for 6 hours. The reaction mixture is then poured in water and extracted with dichloromethane. The organic phase is dried over magnesium sulfate and the solvent evaporated. The compound 5a is obtained as an orange solid after column chromatography (silica, dichloromethane) in 87% yield (0.628 g, 0.66 mmol). H NMR (250 MHz, CD ₂ CI ₂ ) δ 8.43 (s, 4H), 5.06 (m, 2H), 2.22 - 1 .99 (m, 4H), 1 .79 (m, 4H), 1.20 (m, 40 H), 0.82 - 0.69 (m, 12H). FD Mass Spectrum (8kV): m/z= 947.7 (100%) [M+]. Example 3

Preparation of /V,/V'-Bis(1-heptyloctyl)-2,5,8,11 -tetrafluoro-perylene-3,4:9,10-tetracarboxylic acid bisimide (1a)

/V,/V'-Bis(1-heptyloctyl)-2,5,8,1 1 -tetrachloro-perylene-3,4:9,10-tetracarboxylic acid bisimide (5a), prepared as described in example 2, (50 mg, 0.05 mmol) and potassium fluoride (61 mg, 1.05 mmol) are suspended in a mixture of dioxane (2 ml_) and diglyme(1 ml_) and heated in a sealed vessel at 150 °C for 20 hours in a microwave oven. The reaction mixture is then cooled down, the solvent is removed and the remaining solid is purified by column chromatography (silica gel, dichloromethane/petrol ether 2/1 ). The compound 1a is obtained as a yellow solid in 30% yield (13 mg, 002 mmol). H NMR (250 MHz, CD ₂ CI ₂ ) δ 8.23 (d, J = 12.4 Hz, 4 H), 5.15 (m, 2H), 2.18 (m, 4H), 1.82 (m, 4H), 1.25 (m, 40 H), 0.92 - 0.73 (m, 12H). FD Mass Spectrum (8kV): m/z= 947.7 (100%) [M+]. UV-VIS (in dichloromethane): ληΐ3χ: 500 nm. Fluorescence (in dichloromethane, ληΐ3χ: 500 nm): 509 nm.