# US 9,520,565 B2 · Indaceno derivatives as organic semiconductors

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- Number: US 9,520,565 B2
- Document ID: US9520565B2
- Status: Granted
- Kind: B2
- Application number: 14/129,577
- Filed: 2012-05-30
- Published: 2014-05-15
- Granted: 2016-12-13
- Earliest claimed: 2011-06-28
- Assignees: Merck Patent GmbH
- Applicants: Changsheng Wang; Nicolas Blouin; Mansoor D'Lavari; Steven Tierney; Lana Nanson
- Inventors: Changsheng Wang; Nicolas Blouin; Mansoor D'Lavari; Steven Tierney; Lana Nanson
- Web page: https://patentgrep.com/patent/US9520565B2

## CPC

- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- C07D 513/04: Ortho-condensed systems
- H10K 85/6576: {comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene}
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## 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.

## Claims

### Claim 1

A compound comprising one or more divalent units of formula I
wherein
X1 and X2 are independently of each other O, S, Se, Te or CH═CH,
R1 and R2 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—, —NR0—, —SiR0R00—, —CY1═CY2— 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 R1 and R2, 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 R1 and R2 together form an alicyclic group with 1 to 20 C atoms, which is optionally fluorinated or alkylated,
Y1 and Y2 are independently of each other H, F, Cl or CN,
* represents a linkage to an adjacent unit or group, and
R0 and R00 are independently of each other H or optionally substituted C1-40 carbyl or hydrocarbyl.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 2)

The compound according to claim 2, that comprises one or more units of formula II
—[(Ar1)a—(U)b—(Ar2)c—(Ar3)d]— II
wherein
U is a unit of formula I,
Ar1, Ar2, Ar3 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 RS,
RS is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR0R00, —C(O)X0, —C(O)R0, —NH2, —NR0R00, —SH, —SR0, —SO3H, —SO2R0, —OH, —NO2, —CF3, —SF5, 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-,
R0 and R00 are independently of each other H or optionally substituted C1-40 carbyl or hydrocarbyl,
P is a polymerizable or crosslinkable group,
Sp is a spacer group or a single bond,
X0 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.

### Claim 4 (depends on 3)

The compound according to claim 3, additionally comprising one or more repeating units selected of formula III
—[(Ar1)a-(A1)b-(Ar2)c—(Ar3)d]— III
wherein A1 is an aryl or heteroaryl group that is different from U and Ar1-3, has 5 to 30 ring atoms, is optionally substituted by one or more groups RS 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.

### Claim 5 (depends on 4)

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.

### Claim 6 (depends on 5)

The compound according to claim 5, of the following formulae
*—[(Ar1—U—Ar2)x—(Ar3)y]n—* IVa
*—[(Ar1—U—Ar2)x—(Ar3—Ar3)y]n—* IVb
*—[(Ar1—U—Ar2)x—(Ar3—Ar3—Ar3)y]n—* IVc
*—[(Ar1)a—(U)b—(Ar2)c—(Ar3)d]n—* IVd or
*—([(Ar1)a—(U)b—(Ar2)c—(Ar3)d]x—[(Ar1)a-(A1)b-(Ar2)c—(Ar3)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 [(Ar1)a—(U)b—(Ar2)c—(Ar3)d] and in at least one of the repeating units [(Ar1)a-(A1)b-(Ar2)c—(Ar3)d] b is at least 1.

### Claim 7 (depends on 6)

The compound according to claim 6, of the following formulae
wherein R3 and R4 have independently of each other one of the meanings given for R1, and * represents a linkage to an adjacent unit or group.

### Claim 8 (depends on 7)

The compound according to claim 7, of formula V
R5-chain-R6 V
wherein “chain” is a polymer chain selected of formulae IV, R5 and R6 denote, independently of each other, H, F, Br, Cl, I, —CH2Cl, —CHO, —CRa═CRb2, —SiRaRbRc, —SiRaX′X″, —SiRaRbX′, —SnRaRbRc, —BRaRb, —B(ORa)(ORc), —B(OH)2, —O—SO2—Ra, —C≡CH, —C≡C—SiRa3, —ZnX′, —Sn(Z4)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, Ra, Rb and Rc independently of each other denote H or alkyl with 1 to 20 C atoms, and two of Ra, Rb and Rc may also form an aliphatic ring together with the hetero atom to which they are attached, and Z4 is alkyl or aryl, each being optionally substituted.

### Claim 9 (depends on 3)

The compound according to claim 3, wherein one or more of Ar1, Ar2 and Ar3 denote aryl or heteroaryl of the following formulae
wherein one of X11 and X12 is S and the other is Se, and R11, R12, R13, R14, R15, R16, R17 and R18 independently of each other denote H or have one of the meanings of R1, and * represents a linkage to an adjacent unit or group.

### Claim 10 (depends on 4)

The compound according to claim 4, wherein one or more of the units Ar3 and A1 denote aryl or heteroaryl of the following formulae
wherein one of X11 and X12 is S and the other is Se, and R11, R12, R13, R14 and R15 independently of each other denote H or have one of the meanings of R1, and * represents a linkage to an adjacent unit or group.

### Claim 11 (depends on 1)

The compound according to claim 1, of formula VII
Ar4, Ar5 independently of each other and on each occurrence identically or differently aryl or heteroaryl that is different from U, preferably has 5 to 30 ring atoms and is optionally substituted, preferably by one or more groups RS
R7, R8 independently of each other denote H, F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR0R00, —C(O)X0, —C(O)R0, —C(O)OR0, —O—C(O)R0, —NH2, —NR0R00, —SH, —SR0, —SO3H, —SO2R0, —OH, —NO2, —CF3, —SF5, P-Sp-, or optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, and wherein one or more C atoms are optionally replaced by a hetero atom, and R0 and R00 are independently of each other H or optionally substituted C1-40 carbyl or hydrocarbyl, and X0 is halogen and
e and f independently of each other denote 0, 1, 2 or 3.

### Claim 12 (depends on 11)

The compound according to claim 11, which is of formula VIIa

### Claim 13 (depends on 1)

The compound according to claim 1, wherein R1 and R2 independently of each other denote straight-chain, branched or cyclic alkyl with 1 to 20 C atoms which is unsubstituted or substituted by one or more F atoms, or R1 and R2 independently of each other denote aryl or heteroaryl, each of which is optionally fluorinated, alkylated or alkoxylated and has 4 to 30 ring atoms, or one of R1 and R2 denotes H and the other is one of the aforementioned alkyl, aryl or heteroaryl groups, or R1 and R2 together form a cyclic alkyl group with 1 to 20 C atoms, which is unsubstituted or substituted by one or more F atoms or by one or more C1-C10 alkyl groups.

### Claim 14 (depends on 1)

A mixture or blend comprising one or more compounds according to claim 1 and one or more compounds or polymers having semiconducting, charge transport, hole/electron transport, hole/electron blocking, electrically conducting, photoconducting or light emitting properties.

### Claim 15 (depends on 14)

The mixture or blend according to claim 14, further comprising one or more n-type organic semiconductor compounds.

### Claim 16 (depends on 15)

The mixture or blend according to claim 15, wherein the n-type organic semiconductor compound is a fullerene or substituted fullerene.

### Claim 17 (depends on 1)

A formulation comprising one or more compounds, mixtures or blends according to claim 1, and one or more solvents.

### Claim 18 (depends on 11)

A process of preparing a compound or monomer according to claim 11, comprising reacting an indacenodiarene of formula VIII
wherein X is S, O, Se, Te or CH═CH, with an aldehyde or ketone of formula IX
in a Knoevenagel condensation under alkaline conditions.

### Claim 19 (depends on 1)

A charge transport, semiconducting, electrically conducting, photoconducting or light emitting material comprising a compound, mixture, blend or formulation according to claim 1.

### Claim 20 (depends on 1)

An optical, electrooptical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a charge transport, semiconducting, electrically conducting, photoconducting or light emitting material, or comprises a compound, mixture, blend or formulation, according to claim 1.

### Claim 21 (depends on 20)

The optical, electrooptical, electronic, electroluminescent or photoluminescent device according to claim 20, which is selected from organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic solar cells, laser diodes, organic plasmon-emitting diodes (OPEDs), Schottky diodes, organic photoconductors (OPCs) and organic photodetectors (OPDs).

### Claim 22 (depends on 20)

The device according to claim 20, which is an OFET, bulk heterojunction (BHJ) OPV device or inverted BHJ OPV device.

### Claim 23 (depends on 20)

The component according to claim 20, which is selected from charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.

### Claim 24 (depends on 20)

The assembly according to claim 20, which is integrated circuits (IC), radio frequency identification (RFID) tags or security markings or security devices containing them, flat panel displays or backlights thereof, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors or biochips.

### Claim 25 (depends on 1)

In batteries, or in components or devices for detecting and discriminating DNA sequences, the improvement wherein said electrode material containing electrode materials is a compound according to claim 1.

### Claim 26

A monomer of formula VI
R5—Ar1—U—Ar2—R6 VI
wherein U is a unit of formula I
wherein
X1 and X2 are independently of each other O, S, Se, Te or CH═CH,
R1 and R2 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—, —NR0—, —SiR0R00—, —CY1═CY2— 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 R1 and R2, 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 R1 and R2 together form an alicyclic group with 1 to 20 C atoms, which is optionally fluorinated or alkylated,
Y1 and Y2 are independently of each other H, F, Cl or CN,
R0 and R00 are independently of each other H or optionally substituted C1-40 carbyl or hydrocarbyl, Ar1, Ar2 aryl or heteroaryl that is different from U, and is optionally substituted, optionally by one or more groups RS, R5 and R6 are independently of each other, H, F, Br, Cl, I, —CH2Cl, —CHO, —CRa═CRb2, —SiRaRbRc, —SiRaX′X″, —SiRaRbX′, —SnRaRbRc, —BRaRb, —B(ORa)(ORc), —B(OH)2, —O—SO2—Ra, —C≡CH, —C≡C—SiRa3, —ZnX′, —Sn(Z4)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, Ra, Rb and Rc independently of each other denote H or alkyl with 1 to 20 C atoms, and two of Ra, Rb and Rc may also form an aliphatic ring together with the hetero atom to which they are attached, and Z4 is alkyl or aryl, each being optionally substituted, RS is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR0R00, —C(O)X0, —C(O)R0, —NH2, —NR0R00, —SH, —SR0, —SO3H, —SO2R0, —OH, —NO2, —CF3, —SF5, 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-, and at least one of R5 and R6 is different from H, and * represents a linkage to an adjacent unit or group.

### Claim 27 (depends on 2)

A process of preparing a polymer according to claim 2, by coupling one or more monomers of formula VI,
R5—Ar1—U—Ar2—R6 VI
wherein U is a unit of formula I
wherein
X1 and X2 are independently of each other O, S, Se, Te or CH═CH,
R1 and R2 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—, —NR0—, —SiR0R00—, —CY1═CY2— 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, or R1 and R2, 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 R1 and R2 together form an alicyclic group with 1 to 20 C atoms, which is optionally fluorinated or alkylated,
Y1 and Y2 are independently of each other H, F, Cl or CN,
R0 and R00 are independently of each other H or optionally substituted C1-40 carbyl or hydrocarbyl, Ar1, Ar2 aryl or heteroaryl that is different from U, preferably has 5 to 30 ring atoms and is optionally substituted, preferably by one or more groups RS, R5 and R6 are independently of each other, H, F, Br, Cl, I, —CH2Cl, —CHO, —CRa═CRb2, —SiRaRbRc, —SiRaX′X″, —SiRaRbX′, —SnRaRbRc, —BRaRb, —B(ORa)(ORc), —B(OH)2, —O—SO2—Ra, —C≡CH, —C≡C—SiRa3, —ZnX′, —Sn(Z4)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, Ra, Rb and Rc independently of each other denote H or alkyl with 1 to 20 C atoms, and two of Ra, Rb and Rc may also form an aliphatic ring together with the hetero atom to which they are attached, and Z4 is alkyl or aryl, each being optionally substituted, and at least one of R5 and R6 is different from H, wherein R5 and R6 are halogen, stannyl or boronate groups, with each other and/or with one or more monomers of the following formulae
R5—Ar3—R6 C1
R5-A1-R6 C2
wherein Ar3 is aryl or heteroaryl that is different from U, and is optionally substituted, optionally by one or more groups RS, A1 is an aryl or heteroaryl group that is different from U and Ar1-3, has 5 to 30 ring atoms, is optionally substituted by one or more groups RS and is selected from aryl or heteroaryl groups having electron donor properties, RS is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR0R00, —C(O)X0, —C(O)R0, —NH2, —NR0R00, —SH, —SR0, —SO3H, —SO2R0, —OH, —NO2, —CF3, —SF5, 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-, R5 and R6 are halogen, stannyl or boronate groups, in an aryl-aryl coupling reaction.

### Claim 28 (depends on 18)

The process according to claim 18, further comprising adding halogen, trialkylstannyl or boronate groups in 2- and 7-position of the product of the process of claim 18 by i) halogenation with N-halosuccinimide or elemental halogen, or ii) lithiation with alkyllithium and lithium amide, followed by reaction with a halogenation reagent, an alkyl borate, a trialkylstannyl chloride or zinc chloride.