Organic semiconducting compounds
The invention relates to novel organic semiconducting compounds containing a polycyclic unit, to methods for their preparation and educts or intermediates used therein, to compositions, polymer blends and formulations containing them, to the use of the compounds, compositions and polymer blends as organic semiconductors in, or for the preparation of, organic electronic (OE) devices, especially organic photovoltaic (OPV) devices, organic photodetectors (OPD), organic field effect transistors (OFET) and organic light emitting diodes (OLED), and to OE, OPV, OPD, OFET and OLED devices comprising these compounds, compositions or polymer blends.
1. A compound of formula I
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
Ar 1-3 are, each independently, arylene or heteroarylene that has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
Ar 4,5 are, each independently, arylene or heteroarylene that has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L, or CY 1 ═CY 2 or —C≡C—,
Y 1 , Y 2 are, each independently, H, F, Cl or CN,
U 1 is CR 1 R 2 , SiR 1 R 2 , GeR 1 R 2 , NR 1 or C═O,
U 2 is CR 3 R 4 , SiR 3 R 4 , GeR 3 R 4 , NR 3 or C═O,
R 1-4 are, each independently, H, F, Cl or straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or —CN, and in which one or more OH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
and a pair of R 1 and R 2 and/or a pair of R 3 and R 4 together with the C, Si or Ge atom to which they are attached, may also form a spiro group with 5 to 20 ring atoms which is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L
R T1 , R T2 are, each independently a carbyl or hydrocarbyl group with 1 to 30 C atoms that is optionally substituted by one or more groups L and optionally comprises one or more hetero atoms,
and wherein at least one of R T1 and R T2 is an electron withdrawing group,
L is F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or is —O—C(═O)—OR 0 ,
R 0 , R 00 is H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated,
X 0 is halogen,
a, b are, each independently, 0, 1, 2 or 3, and
m is 1, 2 or 3.
2. The compound according to claim 1 , wherein Ar 1-5 in formula I are selected from the following formulae and their mirror images
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
U 1 is CR 1 R 2 , SiR 1 R 2 , GeR 1 R 2 , NR 1 or C═O,
R 1-2 are each independently H, F, Cl or straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or —CN, and in which one or more CH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
and a pair of R 1 and R 2 together with the C, Si or Ge atom to which they are attached, may also form a spiro group with 5 to 20 ring atoms which is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L
W 1,2 are each independently S, O, Se or C═O,
V 1 is CR 5 or N,
V 2 is CR 6 or N,
R 5-10 are each independently H, F, Cl, —CN or straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or —CN, and in which one or more OH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
Y 1 , Y 2 are each independently H, F, Cl or CN,
L is F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or is —O—C(═O)—OR 0 ,
R 0 , R 00 are each independently H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, and
X 0 is halogen.
3. The compound according to claim 1 , wherein Ar 1-3 in formula I are selected from the following formulae and their mirror images
wherein
U 1 is CR 1 R 2 , SiR 1 R 2 , GeR 1 R 2 , NR 1 or C═O, and
R 1-2 are, each independently, H, F, Cl or straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or —CN, and in which one or more CH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
and a pair of R 1 and R 2 together with the C, Si or Ge atom to which they are attached, may also form a spiro group with 5 to 20 ring atoms which is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L
R 5-10 are, each independently, H, F, Cl, —CN or straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or —CN, and in which one or more CH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
Y 1 , Y 2 are, each independently, H, F, Cl or CN,
L are, each independently, F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 0 , —OH, —NO 2 , —CF 3 —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or is —O—C(═O)—OR 0 ,
R 0 , R 00 are, each independently, H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, and
X 0 is halogen.
4. The compound according to claim 1 , wherein Ar 4 and Ar 5 in formula I are selected from the following formulae and their mirror images
wherein
X 1 and X 2 are, each independently, H, F, Cl or straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or —CN, and in which one or more OH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
Y 1 , Y 2 are, each independently, H, F, Cl or CN,
L is F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or is —O—C(═O)—OR 0 ,
R 0 , R 00 are, each independently, H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated,
X 0 is halogen.
5. The compound according to claim 1 , wherein R T1 and R T2 are H, F, Cl, Br, —NO 2 , —CN, —CF 3 , R*, —CF 2 —R*, —O—R*, —S—R*, —SO 2 —R*, —SO 3 —R*, —C(═O)—H, —C(═O)—R*, —C(═S)—R*, —C(═O)—CF 2 —R*, —C(═O)—OR*, —C(═S)—OR*, —O—C(═O)—R*, —O—C(═S)—R*, —C(═O)—SR*, —S—C(═O)—R*, —C(═O)NR*R**, —NR*—C(═O)—R*, —NHR*, —NR*R**, —CR*═CR*R**, —C≡C—R*, —C≡C—SiR*R**R***, —SiR*R**R***, —CH═CH(CN), —CH═C(CN) 2 , —C(CN)═C(CN) 2 , —CH═C(CN)(R a ), CH═C(CN)—C(═O)—OR*, —CH═C(CO—OR*) 2 , —CH═C(CO—NR*R**) 2 , or a group from the following formulae
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
R a , R b are, each independently, aryl or heteroaryl, each having from 4 to 30 ring atoms, optionally containing fused rings and being unsubstituted or substituted with one or more groups L, or one of the meanings given for L,
R*, R**, R*** are, each independently, alkyl with 1 to 20 C atoms which is straight-chain, branched or cyclic, and is unsubstituted, or substituted with one or more F or Cl atoms or CN groups, or perfluorinated, and in which one or more C atoms are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —SiR 0 R 0 —, —NR 0 R 00 —, —CHR 0 ═CR 00 — or —C≡C— such that O- and/or S-atoms are not directly linked to each other,
L is F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or is —O—C(═O)—OR 0 ,
L′ is H or one of the meanings of L,
R 0 , R 00 are, each independently, H or straight-chain or branched alkyl with 1 to 12 C atoms that is optionally fluorinated,
Y 1 , Y 2 are, each independently, H, F, Cl or CN,
X 0 is halogen,
r is 0, 1, 2, 3 or 4,
s is 0, 1, 2, 3, 4 or 5,
t is 0, 1, 2 or 3, and
u is 0, 1 or 2.
6. The compound according to claim 1 , wherein both R T1 and R T2 denote an electron withdrawing group.
7. The compound according to claim 1 , wherein R T1 and R T2 are of the following formulae
wherein
L is F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or is —O—C(═O)—OR 0 ,
R 0 , R 00 are, each independently, H or straight-chain or branched alkyl with 1 to 12 C atoms that is optionally fluorinated,
Y 1 , Y 2 are, each independently, H, F, Cl or CN,
X 0 is halogen,
r is 0, 1, 2, 3 or 4, and
s is 0, 1, 2, 3, 4 or 5.
8. The compound according to claim 1 , which is of the following formulae
wherein
Ar 4,5 are, each independently, arylene or heteroarylene that has from 5 to 20 ring atoms, is mono- or polycyclic, optionally contains fused rings, and is unsubstituted or substituted by one or more identical or different groups L, or CY 1 ═CY 2 or —C≡C—,
Y 1 , Y 2 are, each independently, H, F, Cl or CN,
R 1-4 are, each independently, H, F, Cl or straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or —CN, and in which one or more CH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
and a pair of R 1 and R 2 and/or a pair of R 3 and R 4 together with the C, Si or Ge atom to which they are attached, may also form a spiro group with 5 to 20 ring atoms which is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
R T1 , R T2 are, each independently, a carbyl or hydrocarbyl group with 1 to 30 C atoms that is optionally substituted by one or more groups L and optionally comprises one or more hetero atoms,
and wherein at least one of R T1 and R T2 is an electron withdrawing group,
L is F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or is —O—C(═O)—OR 0 ,
R 0 , R 00 are, each independently, H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated,
X 0 is halogen, and
a, b are, each independently 0, 1, 2 or 3.
9. The compound according to claim 1 , wherein
R 1-4 are each independently alkyl or alkoxy with 1 to 16 C atoms which is optionally fluorinated or aryl or heteroaryl that is mono- or polycyclic, optionally contains fused rings, has 4 to 30 ring atoms, and is optionally substituted by one or more groups L,
L is F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or is —O—C(═O)—OR 0 ,
R 0 , R 00 are, each independently, H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, and
X 0 is halogen.
10. A composition comprising one or more compounds according to claim 1 , and further comprising one or more compounds having one or more of a semiconducting, hole or electron transporting, hole or electron blocking, electrically conducting, photoconducting, photoactive or light emitting properties, and/or a binder.
11. The composition, comprising one or more compounds having one or more of a semiconducting, hole or electron transporting, hole or electron blocking, electrically conducting, photoconducting, photoactive or light emitting properties, and/or a binder, and one or more n-type semiconductors, at least one of which is a compound according to claim 1 , and one or more p-type semiconductors.
12. The composition of claim 10 , comprising one or more p-type semiconductors selected from conjugated polymers.
13. The composition of claim 12 , wherein the conjugated polymers are of the following formulae
wherein R 11-19 independently of each other denote H or have one of the meanings of L,
L is F, Cl, —NO 2 , —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or is —O—C(═O)—OR 0 ,
R 0 , R 00 are, each independently, H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated,
X 0 is halogen,
X 1 , X 2 , X 3 and X 4 each independently denote H, F or Cl,
x and y are each, independently of one another >0 and <1, with x+y=1, and
n is an integer >1.
14. The composition according to claim 10 , comprising one or more n-type semiconductors selected from fullerenes or fullerene derivatives.
15. A bulk heterojunction (BHJ) formed from a composition according to claim 10 .
16. A formulation comprising one or more compounds according to claim 1 , or a composition comprising said one or more compounds and one or more compounds having one or more of a semiconducting, hole or electron transporting, hole or electron blocking, electrically conducting, photoconducting, photoactive or light emitting properties, and/or a binder, and one or more organic solvents.
17. An electronic or optoelectronic device, or a component thereof, or an assembly comprising it, which comprises a compound according to claim 1 , or a composition comprising compound and one or more compounds having one or more of a semiconducting, hole or electron transporting, hole or electron blocking, electrically conducting, photoconducting, photoactive or light emitting properties, and/or a binder.
18. The electronic or optoelectronic device according to claim 17 , which is selected from the group consisting of organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic light emitting electro-chemical cells (OLEC), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, dye-sensitized solar cells (DSSC), perovskite-based solar cells, organic photoelectrochemical cells (OPEC), laser diodes, Schottky diodes, photoconductors, photodetectors, thermoelectric devices and LC windows.
19. The component according to claim 17 , which is selected from the group consisting of charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.
20. The assembly according to claim 17 , which is selected from the group consisting of integrated circuits (IC), radio frequency identification (RFID) tags, security markings, security devices, flat panel displays, backlights of flat panel displays, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips.