# US 8,785,004 B2 · UV light-emissive fluorene-based copolymers

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- Number: US 8,785,004 B2
- Document ID: US8785004B2
- Status: Granted
- Kind: B2
- Application number: 13/146,398
- Filed: 2009-01-30
- Published: 2011-11-17
- Granted: 2014-07-22
- Earliest claimed: 2009-01-30
- Assignees: Hewlett-Packard Development Company, L.P.
- Applicants: Zhang-Lin Zhou; Chung Ching Yang; Lihua Zhao
- Inventors: Zhang-Lin Zhou; Chung Ching Yang; Lihua Zhao
- Web page: https://patentgrep.com/patent/US8785004B2

## CPC

- H10K 85/151: {Copolymers}
- C08G 61/02: Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G 61/12: Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C09B 69/008: {Dyes containing a substituent, which contains a silicium atom}
- C09B 69/109: {containing other specific dyes}
- H10K 85/115: {Polyfluorene; Derivatives thereof}
- C08G 2261/314: Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G 2261/3142: fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
- C08G 2261/316: bridged by heteroatoms, e.g. N, P, Si or B
- C08G 2261/3162: Arylamines
- C08G 2261/5222: electrofluorescent
- Y10S 428/917: Electroluminescent
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

A fluorene-based copolymer of formula I includes a monomeric unit that includes a fluorene group and at least one steric hindering chemical group to provide sufficient steric interaction such that the spatial conformation of the fluorene-based copolymer is substantially non-planar. The fluorene-based copolymer exhibits UV light emission.

## Claims

### Claim 1

A fluorene-based copolymer of the formula:
wherein:
R1 are each independently a steric hindering group,
Q is one or more fused aromatic rings,
D is a group comprising an atom that is one of divalent, trivalent and tetravalent, wherein one valency of the atom is filled by an aromatic moiety attached to Q, and wherein the aromatic moiety has a steric hindering group attached thereto, and wherein remaining valencies of the atom are filled with aromatic substituents, and
n is an integer selected between 2 and 10,000,
wherein the steric hindering groups of R1 and D provide sufficient steric interaction such that the spatial conformation of formula I is non-planar, and
wherein the copolymer exhibits UV light emission.

### Claim 2 (depends on 1)

The fluorene-based copolymer of claim 1, wherein R1 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl.

### Claim 3 (depends on 1)

A fluorene-based copolymer of claim 1, wherein Q is one or more fused aromatic rings, which comprise at least one steric hindering group.

### Claim 4 (depends on 1)

The fluorene-based copolymer of claim 1, wherein D is selected from the group consisting of
wherein the arrow indicates a point of attachment to Q, and wherein
X is O, S, Te, or Se,
Y is N or P,
Z is C or S1,
R2 is selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
R3 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl.

### Claim 5 (depends on 1)

The fluorene-based copolymer of claim 1 having the formula:
wherein
X is O, S, Te, or Se,
R1, R2 and R6 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000;
or having the formula:
wherein
Y is N or P,
R1, R2 and R6 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl,
R3 is selected from the group consisting of hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000;
or having the formula:
wherein
Z is C or S1,
R1, R2 and R6 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl,
R3 is selected from the group consisting of hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000;
or having the formula:
wherein
X is O, S, Te, or Se,
R1, R2, R7, R8 and R9 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000;
or having the formula:
wherein
Y is N or P,
R1, R2, R7, R8 and R9 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl,
R3 is selected from the group consisting of hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000;
or having the formula:
wherein
Z is C or S1,
R1, R2, R7, R8 and R9 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl,
R3 is selected from the group consisting of hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000;
or having the formula:
wherein
X is O, S, Te, or Se,
R1, R2, R10 and R11 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000;
or having the formula:
wherein
Y is N or P,
R1, R2, R10, and R11 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl,
R3 is selected from the group consisting of hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy (such as, e.g., phenoxy), C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000;
or having the formula:
wherein
Z is C or S1,
R1, R2, R10 and R11 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl,
R3 is selected from the group consisting of hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000.

### Claim 6 (depends on 1)

A light-emitting device comprising the fluorene-based copolymer of claim 1.

### Claim 7 (depends on 6)

The device of claim 6 wherein the fluorene-based copolymer is in the form of a layer disposed between two electrodes.

### Claim 8

A light emitting device comprising:
(a) a first electrode;
(b) a second electrode; and
(c) a polymeric layer disposed between the first electrode and the second electrode, wherein the polymeric layer comprises a fluorene-based copolymer of the formula:
wherein
R1 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl,
Q is one or more fused aromatic rings,
D is a group comprising an atom that is one of divalent, trivalent and tetravalent, wherein one valency of the atom is filled by an aromatic group attached to Q, and wherein the aromatic group has a steric hindering group attached thereto, and wherein remaining valencies of the atom are filled with aromatic substituents, and
n is an integer selected between 2 and 10,000.

### Claim 9 (depends on 8)

The device of claim 8, wherein the aromatic group and the aromatic substituents are phenyl.

### Claim 10 (depends on 8)

The device of claim 8, wherein D is a group comprising an atom that is one of divalent, trivalent and tetravalent, wherein one valency of the atom is filled by an aromatic moiety attached to Q at a position that is para to a point of attachment of the atom, and wherein the aromatic moiety has a steric hindering group at a position that is ortho to a point of attachment of the aromatic moiety to Q, and wherein remaining valencies of the atom are filled with aromatic substituents.

### Claim 11 (depends on 8)

The device of claim 8, wherein D is selected from the group consisting of
wherein the arrow indicates a point of attachment to Q, and wherein
X is O, S, Te, or Se,
Y is N or P,
Z is C or Si,
R2 is selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl,
R3 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000.

### Claim 12 (depends on 8)

The device of claim 8, wherein D is selected from the group consisting of
wherein the arrows indicate a point of attachment to in the fluorene-based copolymer, and wherein
X is O, S, Te, or Se,
Y is N or P,
Z is C or Si,
R2 is selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl,
R3 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000.

### Claim 13

A method for forming a fluorene-based copolymer that exhibits enhanced emission properties and stability compared to a fluorene-based polymer that has a planar spatial conformation, the method comprising forming the fluorene-based copolymer from a monomeric unit that comprises a fluorene group and at least one chemical group having a sterically hindered structure, wherein the chemical group renders the spatial conformation of the fluorene-based copolymer non-planar and wherein the chemical group comprises a one or more fused aromatic rings, and (b) a moiety selected from the group consisting of
wherein the arrows indicate a point of attachment in the fluorene-based copolymer, and wherein
X is O, S, Te, or Se,
Y is N or P,
Z is C or Si,
R2 is selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein
R4 and R5 are each independently selected from the group consisting of C1-C30 alkyl and C5-C30 aryl,
R3 are each independently selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C1-C30 alkoxy, C2-C30 alkenoxy, C2-C30 alkynoxy, C5-C30 aryloxy, C1-C30 thioalkyl, C2-C30 thioalkenyl, C2-C30 thioalkynyl, C5-C30 thioaryl, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyl, carboxylate and hydroxy, wherein R4 and R5 are each independently selected from the group consisting of hydrogen, C1-C30 alkyl and C5-C30 aryl, and
n is an integer selected between 2 and 10,000.