# US 10,483,466 B2 · P-doping cross-linking of organic hole transporters

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- Number: US 10,483,466 B2
- Document ID: US10483466B2
- Status: Granted
- Kind: B2
- Application number: 15/316,211
- Filed: 2015-05-28
- Published: 2018-07-12
- Granted: 2019-11-19
- Earliest claimed: 2014-06-03
- Assignees: Siemens Aktiengesellschaft
- Applicants: Siemens Aktiengesellschaft
- Inventors: Guenter Schmid; Anna Maltenberger; Sebastien Pecqueur
- Web page: https://patentgrep.com/patent/US10483466B2

## CPC

- H10K 85/146: {poly N-vinylcarbazol; Derivatives thereof}
- H10K 30/86: Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
- H10K 50/15: Hole transporting layers
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- H10K 85/1135: {Polyethylene dioxythiophene [PEDOT]; Derivatives thereof}
- H10K 85/30: Coordination compounds
- H10K 85/321: {Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]}
- H10K 10/484: {characterised by the channel regions}
- H10K 30/40: comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
- H10K 30/50: Photovoltaic [PV] devices
- Y02E 10/549: Organic PV cells
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A method for producing hole-transporting electrical layers includes reacting a functionalized organic matrix compound with at least one cross-linking reagent on a substrate, which thereby forms higher-molecular-weight compounds. The functionalized organic matrix compound may include particular constituents arranged in a particular chemical formula.

## Claims

### Claim 1

A method for producing hole-transporting electrical layers, the method comprising:
providing a substrate;
providing at least one crosslinking reagent; and
reacting a functionalized organic matrix compound with the at least one crosslinking reagent on the substrate to form compounds of relatively high molecular mass,
wherein the functionalized organic matrix compound conforms to formula 1:
where:
L is a bond or is selected from the group consisting of substituted or nonsubstituted, saturated or unsaturated C1-C50 alkyl, aryl, polyethylene glycol, polyethylenediamine, polyester, polyurethane, polyvinylidenephenyl chains, and mixtures thereof;
E1, E2 independently of one another may be oxygen, sulfur, selenium, NH or NE3,
optionally E3, wherein E3 is selected from the group consisting of substituted or nonsubstituted alkyl and aryl, and E3 is bound to R as follows:
R is selected from the group consisting of H, D, C1-C10 alkyl-silyl or aryl-silyl esters, fluorinated or nonfluorinated branched or unbranched C1-C10 alkyl, aryl, and heteroaryl,
RHTL is selected from the group consisting of PEDOT (poly(3,4-ethylenedioxythiophene)), PVK (poly(9-vinylcarbazole)), PTPD (poly(N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine)), PANI (polyaniline), P3HT (poly(3-hexylthiophene)), and mixtures thereof, and
the crosslinking reagent comprises at least one metal atom from groups 13-15 and at least one organic ligand.

### Claim 2 (depends on 1)

The method of claim 1, wherein E1 and E2 are oxygen.

### Claim 3 (depends on 1)

The method of claim 1, wherein the crosslinking reagent comprises metal atoms from the group consisting of bismuth, tin, lead, and mixtures thereof.

### Claim 4 (depends on 1)

The method of claim 1, where the crosslinking reagent comprises bismuth or tin and at least one ligand of the crosslinking reagent is selected from the group consisting of substituted or nonsubstituted C1-C200 aryl, alkyl, alkoxy, cycloalkyl, arylenes, haloaryl, heteroaryl, heteroarylenes, heterocycloalkylenes, heterocycloalkyl, haloheteroaryl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, ketoaryl, haloketoaryl, ketoheteroaryl, ketoalkyl, haloketoalkyl, ketoalkenyl, and haloketoalkenyl, and, in the case of appropriate radicals, one or more nonadjacent CH2 groups independently of one another may be replaced by —O—, —S—, —NH—, —SiRoRoo—, —CO—, —COO—, —OCO—, —OCO—O—, —SO2—, —S—CO—, —CO—S—, —C═C— or —C≡C—, such that O and/or S atoms are not joined directly to one another.

### Claim 5 (depends on 1)

The method of claim 1, wherein the crosslinking reagent comprises at least one substituent according to formula 2:
where n=0-20.

### Claim 6 (depends on 1)

The method of claim 1, wherein the crosslinking reagent comprises bismuth or tin and comprises at least one substituent with the following structure:
wherein each of Y1 through Y7 is independently selected from the group consisting of C—H, C-D, C—F, C—CF3, C—NO2, C—CN, C—Cl, C—Br, C—CN3, C—OCN, C—NCO, C—CNO, C—SCN, C—NCS, and C—SeCN.

### Claim 7 (depends on 1)

The method of claim 1, wherein the crosslinking reagent comprises at least one substituent selected from the group of 2-(trifluoromethyl)benzoate; 3,5-difluorobenzoate; 3-hydroxy-2,4,6-triiodobenzoate; 3-fluoro-4-methylbenzoate; 3-(trifluoromethoxy)benzoate; 4-(trifluoromethoxy)benzoate; 4-chloro-2,5-difluorobenzoate; 2-chloro-4,5-difluorobenzoate; 2,4,5-trifluorobenzoate; 2-fluorobenzoate; 4-fluorobenzoate; 2,3,4-trifluorobenzoate; 2,3,5-trifluorobenzoate; 2,3-difluorobenzoate; 2,4-bis(trifluoromethyl)benzoate; 2,4-difluorobenzoate; 2,5-difluorobenzoate; 2,6-bis(trifluoromethyl)benzoate; 2,6-difluorobenzoate; 2-chloro-6-fluorobenzoate; 2-fluoro-4-(trifluoromethyl)benzoate; 2-fluoro-5-(trifluoromethyl)benzoate; 2-fluoro-6-(trifluoromethyl)-benzoate; 3,4,5-trifluorobenzoate; 3,4-difluorobenzoate; 3,5-bis(trifluoromethyl)benzoate; 3-(trifluoromethyl)benzoate; 3-chloro-4-fluorobenzoate; 3-fluoro-5-(trifluoromethyl)benzoate; 3-fluorobenzoate; 4-fluoro-2-(trifluoromethyl)benzoate; 4-fluoro-3-(trifluoromethyl)benzoate; 5-fluoro-2-methylbenzoate; 2-(trifluoromethoxy)benzoate; 2,3,5-trichlorobenzoate; 4-(trifluoromethyl)benzoate; pentafluorobenzoate; 2,3,4,5-tetrafluorobenzoate; 2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzoate; 2-fluorophenyl acetate; 3-fluorophenyl acetate; 4-fluorophenyl acetate; 2,3-difluorophenyl acetate; 2,4-difluorophenyl acetate; 2,6-difluorophenyl acetate; 3,4-difluorophenyl acetate; 3,5-difluorophenyl acetate; pentafluorophenyl acetate; 2-chloro-6-fluorophenyl acetate; 2-chloro-3,6-difluorophenyl acetate; 3-chloro-2,6-difluorophenyl acetate; 3-chloro-4-fluorophenyl acetate; 5-chloro-2-fluorophenyl acetate; 2,3,4-trifluorophenyl acetate; 2,3,5-trifluorophenyl acetate; 2,3,6-trifluorophenyl acetate; 2,4,5-trifluorophenyl acetate; 2,4,6-trifluorophenyl acetate; 3,4,5-trifluorophenyl acetate; 3-chloro-2-fluorophenyl acetate; α-fluorophenyl acetate; 4-chloro-2-fluorophenyl acetate; 2-chloro-4-fluorophenyl acetate; α,α-difluorophenyl acetate; ethyl 2,2-difluoro-2-phenyl acetate; methyl trifluoroacetate; allyl trifluoroacetate; ethyl trifluoroacetate; isopropyl trifluoroacetate; 2,2,2-trifluoroethyl trifluoroacetate; difluoroacetate; trifluoroacetate; methyl chlorodifluoroacetate; ethyl bromo-difluoroacetate; chlorodifluoroacetate; ethyl chlorofluoroacetate; ethyl difluoroacetate; (3-chlorophenyl)difluoroacetate; (3,5-difluorophenyl)difluoroacetate; (4-dimethylphenyl)difluoroacetate; (3-chloro-4-fluorophenyl)difluoroacetate; (4-chlorophenyl)difluoroacetate; 2-biphenylyl-3′,5′-difluoroacetate; 3-biphenylyl-3′,5′-difluoroacetate; 4-biphenylyl-3′,5′-difluoroacetate; 2-biphenylyl-3′,4′-difluoroacetate; 3-biphenylyl-3′,4′-difluoroacetate; 4-biphenylyl-3′,4′-difluoroacetate, and 2,2-difluoropropionate.

### Claim 8 (depends on 1)

The method of claim 1, wherein the crosslinking reagent comprises bismuth or tin and includes at least one substituent selected from the group consisting of 2,6-difluorobenzoate, 4-fluorobenzoate, 3-fluorobenzoate, 3,5-difluorobenzoate, 3,4,5-trifluorobenzoate, 3,5-bis(trifluoromethyl)benzoate, perfluorobenzoate, 4-perfluorotoluate, and mixtures thereof.

### Claim 9 (depends on 1)

The method of claim 1, wherein the crosslinking reagent is a substituted or nonsubstituted triaryl-bismuth complex.

### Claim 10 (depends on 1)

The method of claim 1, wherein the crosslinking reagent and the organic matrix compound are reacted on the substrate using a temperature treatment in a range of greater than or equal to 50° C. and less than or equal to 300° C.

### Claim 11 (depends on 1)

The method of claim 1, wherein the functionalized organic matrix compound comprises a further fraction of greater than or equal to 0 weight % and less than or equal to 50 weight % of nonfunctionalized matrix compound.

### Claim 12

A method for producing hole-transporting electrical layers, the method comprising:
providing a substrate;
providing at least one crosslinking reagent; and
reacting a functionalized organic matrix compound with the at least one crosslinking reagent on the substrate to form compounds of relatively high molecular mass,
wherein the functionalized organic matrix compound conforms to formula 1:
where:
L is a bond or is selected from the group consisting of substituted or nonsubstituted, saturated or unsaturated C1-C50 alkyl, aryl, polyethylene glycol, polyethylenediamine, polyester, polyurethane, polyvinylidenephenyl chains, and mixtures thereof;
E1, E2 independently of one another may be oxygen, sulfur, selenium, NH or NE3,
optionally E3, wherein E3 is selected from the group consisting of substituted or nonsubstituted alkyl and aryl, and E3 is bound to R as follows:
R is selected from the group consisting of H, D, C1-C10 alkyl-silyl or aryl-silyl esters, fluorinated or nonfluorinated branched or unbranched C1-C10 alkyl, aryl, and heteroaryl,
RHTL is selected from the group consisting of C20-C200 triarylamine-based hole transporters, thiophene-containing derivatives thereof, and mixtures thereof, and
the crosslinking reagent comprises at least one metal atom from groups 13-15 and at least one organic ligand.

### Claim 13 (depends on 12)

The method of claim 12, wherein E1 and E2 are oxygen.

### Claim 14 (depends on 12)

The method of claim 12, wherein the crosslinking reagent comprises metal atoms from the group consisting of bismuth, tin, lead, and mixtures thereof.

### Claim 15 (depends on 12)

The method of claim 12, where the crosslinking reagent comprises bismuth or tin and at least one ligand of the crosslinking reagent is selected from the group consisting of substituted or nonsubstituted C1-C200 aryl, alkyl, alkoxy, cycloalkyl, arylenes, haloaryl, heteroaryl, heteroarylenes, heterocycloalkylenes, heterocycloalkyl, haloheteroaryl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, ketoaryl, haloketoaryl, ketoheteroaryl, ketoalkyl, haloketoalkyl, ketoalkenyl, and haloketoalkenyl, and, in the case of appropriate radicals, one or more nonadjacent CH2 groups independently of one another may be replaced by —O—, —S—, —NH—, —NRo—, —SiRoRoo—, —CO—, —COO—, —OCO—, —OCO—O—, —SO2—, —S—CO—, —CO—S—, —C═C— or —C≡C—, such that O and/or S atoms are not joined directly to one another.

### Claim 16 (depends on 12)

The method of claim 12, wherein the crosslinking reagent comprises at least one substituent according to formula 2:
where n=0-20.

### Claim 17 (depends on 12)

The method of claim 12, wherein the crosslinking reagent comprises bismuth or tin and comprises at least one substituent with the following structure:
wherein each of Y1 through Y7 is independently selected from the group consisting of C—H, C-D, C—F, C—CF3, C—NO2, C—CN, C—Cl, C—Br, C—CN3, C—OCN, C—NCO, C—CNO, C—SCN, C—NCS, and C—SeCN.

### Claim 18 (depends on 12)

The method of claim 12, wherein the crosslinking reagent comprises at least one substituent selected from the group of 2-(trifluoromethyl)benzoate; 3,5-difluorobenzoate; 3-hydroxy-2,4,6-triiodobenzoate; 3-fluoro-4-methylbenzoate; 3-(trifluoromethoxy)benzoate; 4-(trifluoromethoxy)benzoate; 4-chloro-2,5-difluorobenzoate; 2-chloro-4,5-difluorobenzoate; 2,4,5-trifluorobenzoate; 2-fluorobenzoate; 4-fluorobenzoate; 2,3,4-trifluorobenzoate; 2,3,5-trifluorobenzoate; 2,3-difluorobenzoate; 2,4-bis(trifluoromethyl)benzoate; 2,4-difluorobenzoate; 2,5-difluorobenzoate; 2,6-bis(trifluoromethyl)benzoate; 2,6-difluorobenzoate; 2-chloro-6-fluorobenzoate; 2-fluoro-4-(trifluoromethyl)benzoate; 2-fluoro-5-(trifluoromethyl)benzoate; 2-fluoro-6-(trifluoromethyl)benzoate; 3,4,5-trifluorobenzoate; 3,4-difluorobenzoate; 3,5-bis(trifluoromethyl)benzoate; 3-(trifluoromethyl)benzoate; 3-chloro-4-fluorobenzoate; 3-fluoro-5-(trifluoromethyl)benzoate; 3-fluorobenzoate; 4-fluoro-2-(trifluoromethyl)benzoate; 4-fluoro-3-(trifluoromethyl)benzoate; 5-fluoro-2-methylbenzoate; 2-(trifluoromethoxy)benzoate; 2,3,5-trichlorobenzoate; 4-(trifluoromethyl)benzoate; pentafluorobenzoate; 2,3,4,5-tetrafluorobenzoate; 2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzoate; 2-fluorophenyl acetate; 3-fluorophenyl acetate; 4-fluorophenyl acetate; 2,3-difluorophenyl acetate; 2,4-difluorophenyl acetate; 2,6-difluorophenyl acetate; 3,4-difluorophenyl acetate; 3,5-difluorophenyl acetate; pentafluorophenyl acetate; 2-chloro-6-fluorophenyl acetate; 2-chloro-3,6-difluorophenyl acetate; 3-chloro-2,6-difluorophenyl acetate; 3-chloro-4-fluorophenyl acetate; 5-chloro-2-fluorophenyl acetate; 2,3,4-trifluorophenyl acetate; 2,3,5-trifluorophenyl acetate; 2,3,6-trifluorophenyl acetate; 2,4,5-trifluorophenyl acetate; 2,4,6-trifluorophenyl acetate; 3,4,5-trifluorophenyl acetate; 3-chloro-2-fluorophenyl acetate; α-fluorophenyl acetate; 4-chloro-2-fluorophenyl acetate; 2-chloro-4-fluorophenyl acetate; α,α-difluorophenyl acetate; ethyl 2,2-difluoro-2-phenyl acetate; methyl trifluoroacetate; allyl trifluoroacetate; ethyl trifluoroacetate; isopropyl trifluoroacetate; 2,2,2-trifluoroethyl trifluoroacetate; difluoroacetate; trifluoroacetate; methyl chlorodifluoroacetate; ethyl bromo-difluoroacetate; chlorodifluoroacetate; ethyl chlorofluoroacetate; ethyl difluoroacetate; (3-chlorophenyl)difluoroacetate; (3,5-difluorophenyl)difluoroacetate; (4-butylphenyl)difluoroacetate; (4-tert-butylphenyl)difluoroacetate; (3,4-dimethylphenyl)difluoroacetate; (3-chloro-4-fluorophenyl)difluoroacetate; (4-chlorophenyl)difluoroacetate; 2-biphenylyl-3′,5′-difluoroacetate; 3-biphenylyl-3′,5′-difluoroacetate; 4-biphenylyl-3′,5′-difluoroacetate; 2-biphenylyl-3′,4′-difluoroacetate; 3-biphenylyl-3′,4′-difluoroacetate; 4-biphenylyl-3′,4′-difluoroacetate, and 2,2-difluoropropionate.

### Claim 19 (depends on 12)

The method of claim 12, wherein the crosslinking reagent comprises bismuth or tin and includes at least one substituent selected from the group consisting of 2,6-difluorobenzoate, 4-fluorobenzoate, 3-fluorobenzoate, 3,5-difluorobenzoate, 3,4,5-trifluoro-benzoate, 3,5-bis(trifluoromethyl)benzoate, perfluorobenzoate, 4-perfluorotoluate, and mixtures thereof.

### Claim 20

A method for producing hole-transporting electrical layers, the method comprising:
providing a substrate;
providing at least one crosslinking reagent; and
reacting a functionalized organic matrix compound with the at least one crosslinking reagent on the substrate to form compounds of relatively high molecular mass,
wherein the functionalized organic matrix compound conforms to formula 1:
where:
L is a bond or is selected from the group consisting of substituted or nonsubstituted, saturated or unsaturated C1-C50 alkyl, aryl, polyethylene glycol, polyethylenediamine, polyester, polyurethane, polyvinylidenephenyl chains, and mixtures thereof;
E1, E2 independently of one another may be oxygen, sulfur, selenium, NH or NE3,
optionally E3, wherein E3 is selected from the group consisting of substituted or nonsubstituted alkyl and aryl, and E3 is bound to R as follows:
R is selected from the group consisting of H, D, C1-C10 alkyl-silyl or aryl-silyl esters, fluorinated or nonfluorinated branched or unbranched C1-C10 alkyl, aryl, and heteroaryl,
RHTL is a substituted compound functionalized with at least one compound selected from the group consisting of
NPB (N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine),
β-NPB (N,N′-bis(naphthalen-2-yl)-N,N′-bis(phenyl)benzidine),
TPD (N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine),
Spiro TPD (N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine),
Spiro-NPB (N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-spiro),
DMFL-TPD (N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-9,9-dimethylfluorene),
DMFL-NPB (N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-9,9-dimethylfluorene),
DPFL-TPD (N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-9,9-diphenylfluorene),
DPFL-NPB (N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-9,9-diphenylfluorene),
Spiro-TAD (2,2′,7,7′-tetrakis(N,N-diphenylamino)-9,9′-spirobifluorene),
9,9-bis[4-(N,N-bisbiphenyl-4-ylamino)phenyl]-9H-fluorene,
9,9-bis[4-(N,N-bisnaphthalen-2-ylamino)phenyl]-9H-fluorene,
9,9-bis[4-(N,N′-bisnaphthalen-2-yl-N,N′-bisphenylamino)phenyl]-9H-fluorene,
N,N′-bis(phenanthren-9-yl)-N,N′-bis(phenyl)benzidine,
2,7-bis[N,N-bis(9,9-spirobifluoren-2-yl)amino]-9,9-spirobifluorene,
2,2′-bis[N,N-bis(biphenyl-4-yl)amino]-9,9-spirobifluorene,
2,2′-bis(N,N-diphenylamino)-9,9-spirobifluorene,
di[4-(N,N-ditolylamino)phenyl]cyclohexane,
2,2′,7,7′-tetra(N,N-ditolyl)aminospirobifluorene,
N,N,N′,N′-tetranaphthalen-2-ylbenzidine and mixtures thereof, and
the crosslinking reagent comprises at least one metal atom from groups 13-15 and at least one organic ligand;
wherein the crosslinking reagent and the organic matrix compound are reacted on the substrate using a temperature treatment in a range of greater than or equal to 50° C. and less than or equal to 300° C.

### Claim 21 (depends on 20)

The method of claim 20, wherein E1 and E2 are oxygen.

### Claim 22 (depends on 20)

The method of claim 20, wherein the crosslinking reagent comprises metal atoms from the group consisting of bismuth, tin, lead, and mixtures thereof.

### Claim 23 (depends on 20)

The method of claim 20, where the crosslinking reagent comprises bismuth or tin and at least one ligand of the crosslinking reagent is selected from the group consisting of substituted or nonsubstituted C1-C200 aryl, alkyl, alkoxy, cycloalkyl, arylenes, haloaryl, heteroaryl, heteroarylenes, heterocycloalkylenes, heterocycloalkyl, haloheteroaryl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, ketoaryl, haloketoaryl, ketoheteroaryl, ketoalkyl, haloketoalkyl, ketoalkenyl, and haloketoalkenyl, and, in the case of appropriate radicals, one or more nonadjacent CH2 groups independently of one another may be replaced by —O—, —S—, —NH—, —NRo—, —SiRoRoo—, —CO—, —COO—, —OCO—, —OCO—O—, —SO2—, —S—CO—, —CO—S—, —C═C— or —C≡C—, such that O and/or S atoms are not joined directly to one another.

### Claim 24 (depends on 20)

The method of claim 20, wherein the crosslinking reagent comprises at least one substituent according to formula 2:
where n=0-20.

### Claim 25 (depends on 20)

The method of claim 20, wherein the crosslinking reagent comprises bismuth or tin and comprises at least one substituent with the following structure:
wherein each of Y1 through Y7 is independently selected from the group consisting of C—H, C-D, C—F, C—CF3, C—NO2, C—CN, C—Cl, C—Br, C—CN3, C—OCN, C—NCO, C—CNO, C—SCN, C—NCS, and C—SeCN.

### Claim 26 (depends on 20)

The method of claim 20, wherein the crosslinking reagent comprises at least one substituent selected from the group of 2-(trifluoromethyl)benzoate; 3,5-difluorobenzoate; 3-hydroxy-2,4,6-triiodobenzoate; 3-fluoro-4-methylbenzoate; 3-(trifluoromethoxy)benzoate; 4-(trifluoromethoxy)benzoate; 4-chloro-2,5-difluorobenzoate; 2-chloro-4,5-difluorobenzoate; 2,4,5-trifluorobenzoate; 2-fluorobenzoate; 4-fluorobenzoate; 2,3,4-trifluorobenzoate; 2,3,5-trifluorobenzoate; 2,3-difluorobenzoate; 2,4-bis(trifluoromethyl)benzoate; 2,4-difluorobenzoate; 2,5-difluorobenzoate; 2,6-bis(trifluoromethyl)benzoate; 2,6-difluorobenzoate; 2-chloro-6-fluorobenzoate; 2-fluoro-4-(trifluoromethyl)benzoate; 2-fluoro-5-(trifluoromethyl)benzoate; 2-fluoro-6-(trifluoromethyl)benzoate; 3,4,5-trifluorobenzoate; 3,4-difluorobenzoate; 3,5-bis(trifluoromethyl)benzoate; 3-(trifluoromethyl)benzoate; 3-chloro-4-fluorobenzoate; 3-fluoro-5-(trifluoromethyl)benzoate; 3-fluorobenzoate; 4-fluoro-2-(trifluoromethyl)benzoate; 4-fluoro-3-(trifluoromethyl)benzoate; 5-fluoro-2-methylbenzoate; 2-(trifluoromethoxy)benzoate; 2,3,5-trichlorobenzoate; 4-(trifluoromethyl)benzoate; pentafluorobenzoate; 2,3,4,5-tetrafluorobenzoate; 2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzoate; 2-fluorophenyl acetate; 3-fluorophenyl acetate; 4-fluorophenyl acetate; 2,3-difluorophenyl acetate; 2,4-difluorophenyl acetate; 2,6-difluorophenyl acetate; 3,4-difluorophenyl acetate; 3,5-difluorophenyl acetate; pentafluorophenyl acetate; 2-chloro-6-fluorophenyl acetate; 2-chloro-3,6-difluorophenyl acetate; 3-chloro-2,6-difluorophenyl acetate; 3-chloro-4-fluorophenyl acetate; 5-chloro-2-fluorophenyl acetate; 2,3,4-trifluorophenyl acetate; 2,3,5-trifluorophenyl acetate; 2,3,6-trifluorophenyl acetate; 2,4,5-trifluorophenyl acetate; 2,4,6-trifluorophenyl acetate; 3,4,5-trifluorophenyl acetate; 3-chloro-2-fluorophenyl acetate; α-fluorophenyl acetate; 4-chloro-2-fluorophenyl acetate; 2-chloro-4-fluorophenyl acetate; α,α-difluorophenyl acetate; ethyl 2,2-difluoro-2-phenyl acetate; methyl trifluoroacetate; allyl trifluoroacetate; ethyl trifluoroacetate; isopropyl trifluoroacetate; 2,2,2-trifluoroethyl trifluoroacetate; difluoroacetate; trifluoroacetate; methyl chlorodifluoroacetate; ethyl bromo-difluoroacetate; chlorodifluoroacetate; ethyl chlorofluoroacetate; ethyl difluoroacetate; (3-chlorophenyl)difluoroacetate; (3,5-difluorophenyl)difluoroacetate; (4-butylphenyl)difluoroacetate; (4-tert-butylphenyl)difluoroacetate; (3,4-dimethylphenyl)difluoroacetate; (3-chloro-4-fluorophenyl)difluoroacetate; (4-chlorophenyl)difluoroacetate; 2-biphenylyl-3′,5′-difluoroacetate; 3-biphenylyl-3′,5′-difluoroacetate; 4-biphenylyl-3′,5′-difluoroacetate; 2-biphenylyl-3′,4′-difluoroacetate; 3-biphenylyl-3′,4′-difluoroacetate; 4-biphenylyl-3′,4′-difluoroacetate, and 2,2-difluoropropionate.

### Claim 27 (depends on 20)

The method of claim 20, wherein the crosslinking reagent comprises bismuth or tin and includes at least one substituent selected from the group consisting of 2,6-difluorobenzoate, 4-fluorobenzoate, 3-fluorobenzoate, 3,5-difluorobenzoate, 3,4,5-trifluoro-benzoate, 3,5-bis(trifluoromethyl)benzoate, perfluorobenzoate, 4-perfluorotoluate, and mixtures thereof.