Indaceno derivatives as organic semiconductors

Patent metadata

Field	Value
Publication number	US-9520565-B2
Application number	US-201214129577-A
Country	US
Kind code	B2
Filing date	May 30, 2012
Priority date	Jun 28, 2011
Publication date	Dec 13, 2016
Grant date	Dec 13, 2016

Abstract

The invention relates to novel organic semiconducting compounds containing one or more dialkylidene-s-indacenodiheteroarene groups, methods for their preparation and educts or intermediates used therein, polymers, blends, mixtures and formulations containing them, the use of the compounds, polymers, blends, mixtures and formulations as semiconductor in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices, and to OE and OPV devices comprising these compounds, polymers, blends, mixtures or formulations.

First claim

The invention claimed is:

1. A compound comprising one or more divalent units of formula I

wherein
X 1 and X 2 are independently of each other O, S, Se, Te or CH═CH,
R 1 and R 2 independently of each other, and on each occurrence identically or differently, denote H, straight-chain, branched or cyclic alkyl, with 1 to 30 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —NR 0 —, —SiR 0 R 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, or I, or R 1 and R 2 , independently of each other, and on each occurrence identically or differently, denote aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted, or R 1 and R 2 together form an alicyclic group with 1 to 20 C atoms, which is optionally fluorinated or alkylated,
Y 1 and Y 2 are independently of each other H, F, Cl or CN,
* represents a linkage to an adjacent unit or group, and
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl.

2. The compound according to claim 1 , that is a polymer comprising one or more units of formula I as defined in claim 1 .

3. The compound according to claim 2 , that comprises one or more units of formula II
—[(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ]—  II

wherein
U is a unit of formula I,
Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, and is optionally substituted, optionally by one or more groups R S ,
R S is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or P-Sp-,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
P is a polymerizable or crosslinkable group,
Sp is a spacer group or a single bond,
X 0 is halogen,
a, b, c are on each occurrence identically or differently 0, 1 or 2,
d is on each occurrence identically or differently 0 or an integer from 1 to 10,
wherein the polymer comprises at least one repeating unit of formula II wherein b is at least 1.

4. The compound according to claim 3 , additionally comprising one or more repeating units selected of formula III
—[(Ar 1 ) a -(A 1 ) b -(Ar 2 ) c —(Ar 3 ) d ]—  III

wherein A 1 is an aryl or heteroaryl group that is different from U and Ar 1-3 , has 5 to 30 ring atoms, is optionally substituted by one or more groups R S and is aryl or heteroaryl groups having electron donor properties, wherein the polymer comprises at least one repeating unit of formula III wherein b is at least 1.

5. The compound according to claim 4 , of formula IV:

wherein
A is a unit of formula I,
B is a unit that is different from A and comprises one or more aryl or heteroaryl groups that are optionally substituted,
x is >0 and ≦1,
y is ≧0 and <1,
x+y is 1,
n is an integer>1, and * represents a linkage to an adjacent unit or group.

6. The compound according to claim 5 , of the following formulae
*—[(Ar 1 —U—Ar 2 ) x —(Ar 3 ) y ] n —*  IVa

*—[(Ar 1 —U—Ar 2 ) x —(Ar 3 —Ar 3 ) y ] n —*  IVb

*—[(Ar 1 —U—Ar 2 ) x —(Ar 3 —Ar 3 —Ar 3 ) y ] n —*  IVc

*—[(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ] n —*  IVd or

*—([(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ] x —[(Ar 1 ) a -(A 1 ) b -(Ar 2 ) c —(Ar 3 ) d ] y ) n —*  IVe

wherein * represents a linkage to an adjacent unit or group, these polymers can be alternating or random copolymers, and wherein in formula IVd and IVe in at least one of the repeating units [(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ] and in at least one of the repeating units [(Ar 1 ) a -(A 1 ) b -(Ar 2 ) c —(Ar 3 ) d ] b is at least 1.

7. The compound according to claim 6 , of the following formulae

wherein R 3 and R 4 have independently of each other one of the meanings given for R 1 , and * represents a linkage to an adjacent unit or group.

8. The compound according to claim 7 , of formula V
R 5 -chain-R 6   V

wherein “chain” is a polymer chain selected of formulae IV, R 5 and R 6 denote, independently of each other, H, F, Br, Cl, I, —CH 2 Cl, —CHO, —CR a ═CR b 2 , —SiR a R b R c , —SiR a X′X″, —SiR a R b X′, —SnR a R b R c , —BR a R b , —B(OR a )(OR c ), —B(OH) 2 , —O—SO 2 —R a , —C≡CH, —C≡C—SiR a 3 , —ZnX′, —Sn(Z 4 ) 3 , an endcap group, or P-Sp-, wherein P is a polymerizable or crosslinkable group, Sp is a spacer group or a singlebond, X′ and X″ denote halogen, R a , R b and R c independently of each other denote H or alkyl with 1 to 20 C atoms, and two of R a , R b and R c may also form an aliphatic ring together with the hetero atom to which they are attached, and Z 4 is alkyl or aryl, each being optionally substituted.

9. The compound according to claim 3 , wherein one or more of Ar 1 , Ar 2 and Ar 3 denote aryl or heteroaryl of the following formulae

wherein one of X 11 and X 12 is S and the other is Se, and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 independently of each other denote H or have one of the meanings of R 1 , and * represents a linkage to an adjacent unit or group.

10. The compound according to claim 4 , wherein one or more of the units Ar 3 and A 1 denote aryl or heteroaryl of the following formulae

wherein one of X 11 and X 12 is S and the other is Se, and R 11 , R 12 , R 13 , R 14 and R 15 independently of each other denote H or have one of the meanings of R 1 , and * represents a linkage to an adjacent u

Assignees

• Wang Changsheng
• Blouin Nicolas
• D'Lavari Mansoor
• Tierney Steven
• Nanson Lana
• Merck Patent Gmbh

Inventors

• Wang Changsheng
• Blouin Nicolas
• D'Lavari Mansoor
• Tierney Steven
• Nanson Lana

Classifications

• C07D513/04 Primary

  Ortho-condensed systems · CPC title

• H01L51/0074

  Electricity · mapped topic

• H01L51/0036 Primary

  Electricity · mapped topic

• Y02P70/50

  Manufacturing or production processes characterised by the final manufactured product · CPC title

• H10K85/113 Primary

  Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene · CPC title