# US 12,010,914 B2 · Thermally activated delayed fluorescent material based on 9,10-dihydro-9,9-dimethylacridine analogues for prolonging device longevity

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- Number: US 12,010,914 B2
- Document ID: US12010914B2
- Status: Granted
- Kind: B2
- Application number: 17/552,649
- Filed: 2021-12-16
- Published: 2022-04-07
- Granted: 2024-06-11
- Earliest claimed: 2015-08-25
- Assignees: Arizona Board of Regents on behalf of Arizona State University
- Applicants: Arizona Board of Regents on behalf of Arizona State University
- Inventors: Jian Li; Daijun Feng
- Web page: https://patentgrep.com/patent/US12010914B2

## CPC

- H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole}
- C07D 471/06: Peri-condensed systems
- C07D 519/00: Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
- C07F 9/5728: {condensed with carbocyclic rings or carbocyclic ring systems}
- C07F 9/6561: containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
- C09K 11/06: containing organic luminescent materials
- H10K 85/654: {comprising only nitrogen as heteroatom (H10K85/652 takes precedence)}
- C09K 2211/1007: Non-condensed systems
- C09K 2211/1022: bridged by heteroatoms, e.g. N, P, Si or B
- C09K 2211/1029: containing one nitrogen atom as the heteroatom
- C09K 2211/1044: containing two nitrogen atoms as heteroatoms
- C09K 2211/1048: with oxygen
- C09K 2211/1059: containing three nitrogen atoms as heteroatoms
- C09K 2211/1096: containing other heteroatoms
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 85/6565: {Oxadiazole compounds}
- H10K 2101/10: Triplet emission
- H10K 2101/20: Delayed fluorescence emission
- Y02E 10/549: Organic PV cells
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Thermally activated delayed fluorescent compounds and uses thereof are described. The thermally activated delayed fluorescent compounds are an analogues of 9,10-dihydro-9,9-dimethylacridine compounds.

## Claims

### Claim 1

A thermally activated delayed fluorescent composition having the general formula of:
wherein:
independently represents one or more acceptor moieties of the compound that contributes to LUMO level of the compound, where An is nitrogen-containing heteroaryl group, a RqMO group, where M is C, S, P, or As, or a RqSO2 group, or any combination thereof; and n=1, 2, or 3, such that the compound includes a single acceptor moiety (A1), two acceptor moieties (A1 and A2), or three acceptor moieties (A1, A2, and A3), and wherein each acceptor moiety is substituted with Rq:
L1, L2, and L3 are each independently linkage groups comprising an oxygen (O) containing group, a sulfur (S) containing group, a nitrogen (N) containing group, a carbon (C) containing group, a phosphorous (P) containing group, a silicon (Si) containing group, or a boron (B) containing group; wherein at least one of L1, L2, and L3 comprises a boron containing group; and
Rm, Rn, Rp Rq, and Rq′ each independently represent mono-, di-, tri, or tetra-substitution, and each independently are one or more of a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted mono- or dialkylamino group, a substituted or unsubstituted mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.

### Claim 2 (depends on 1)

The composition of claim 1, wherein L1, L2, and L3 are each independently
wherein at least one of L1, L2, and L3 is represented by
wherein R, R1 and R2 each independently represents a hydrogen atom, deuterium, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, a substituted or unsubstituted heterocyclic group, a carbene group, or a N-heterocyclic carbene, or a combination thereof.

### Claim 3 (depends on 2)

The composition of claim 2, wherein L1 is represented by

### Claim 4 (depends on 2)

The composition of claim 2, wherein two of L1, L2, and L3 are represented by

### Claim 5 (depends on 2)

The composition of claim 2, wherein each of L1, L2, and L3 is represented by

### Claim 6 (depends on 2)

The composition of claim 2, wherein in the group
R is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.

### Claim 7 (depends on 1)

The composition of claim 1, wherein An is:
wherein Rq′ has the same definition as Rq.

### Claim 8 (depends on 1)

The composition of claim 1, wherein An is a nitrogen-containing heteroaryl group comprising 1 to 3 nitrogen atoms.

### Claim 9 (depends on 1)

The composition of claim 1, wherein An is
where U, U1, and U2 each independently represents N or C;
with the proviso that at least one of U1 and U2 is N.

### Claim 10 (depends on 1)

The composition of claim 1, wherein An is

### Claim 11 (depends on 1)

The composition of claim 1, wherein n is 2 and the composition has the general structure of:
wherein:
independently represents a second acceptor moiety of the compound that contributes to LUMO level of the compound, where A2 is nitrogen-containing heteroaryl group, a RuMO group, where M is C, S, P, or As, or a RuSO2 group, or any combination thereof; and
Ru is a mono-, di-, tri, or tetra-substitution, and each substitution is one or more of a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted mono- or dialkylamino group, a substituted or unsubstituted mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxy carbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.

### Claim 12 (depends on 1)

The composition of claim 1, wherein n=3, and the composition has the general structure of:
where:
independently represents a second acceptor moiety of the compound that contributes to LUMO level of the compound, where A2 is nitrogen-containing heteroaryl group, a RuMO group, where M is C, S, P, or As, or a RuSO2 group, or any combination thereof;
independently represents a third acceptor moiety of the compound, contributes to LUMO level of the compound, where A3 is nitrogen-containing heteroaryl group, a RvMO group, where M is C, S, P, or As, or a RvSO2 group, or any combination thereof; and
Ru and Rv are each independently a mono-, di-, tri, or tetra-substitution, and each substitution is one or more of a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted mono- or dialkylamino group, a substituted or unsubstituted mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.

### Claim 13 (depends on 1)

The composition of claim 1, having the general structure of:
where:
L3 and L4 are each independently linkage groups comprising an oxygen (O) containing group, a sulfur (S) containing group, a nitrogen (N) containing group, a carbon (C) containing group, a phosphorous (P) containing group, a silicon (Si) containing group, or a boron (B) containing group; and
Rm, Rn, Rs, Rt, each independently represents mono-, di-, tri, or tetra-substitution, and each independently represents one or more of a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted mono- or dialkylamino group, a substituted or unsubstituted mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.

### Claim 14 (depends on 13)

The composition of claim 13, having the general structure:
where L5 and L6 are each independently linkage groups comprising an oxygen (O) containing group, a sulfur (S) containing group, a nitrogen (N) containing group, a carbon (C) containing group, a phosphorous (P) containing group, a silicon (Si) containing group, or a boron (B) containing group; and
Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, and Ri each independently represents mono-, di-, tri, or tetra-substitution, and each independently represents one or more of a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted mono- or dialkylamino group, a substituted or unsubstituted mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxy carbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.

### Claim 15

A thermally activated delayed fluorescent composition having a general structure of:
where:
independently represents one or more acceptor moieties of the compound that contributes to LUMO level of the compound, where An is nitrogen-containing heteroaryl group, a RqMO group, where M is C, S, P, or As, or a RqSO2 group, or any combination thereof; and n=1, 2, or 3, such that the compound includes a single acceptor moiety (A1), two acceptor moieties (A1 and A2), or three acceptor moieties (A1, A2, and A3), and wherein each acceptor moiety is substituted with Rq; and
L1 and L2 are each independently linkage groups comprising an oxygen (O) containing group, a sulfur (S) containing group, a nitrogen (N) containing group, a carbon (C) containing group, a phosphorous (P) containing group, a silicon (Si) containing group, or a boron (B) containing group; wherein at least one of L1 and L2 comprises a boron containing group; and
ring B and ring B2 are each independently a substituted electron-deficient aromatic group,
Rm, Rn, Rp, Rs, and Rt each independently represents mono-, di-, tri, or tetra-substitution, and each independently represents one or more of a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted mono- or dialkylamino group, a substituted or unsubstituted mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.

### Claim 16 (depends on 15)

The composition of claim 15, wherein n=2, and the composition has the general structure of:
wherein
independently represents a second acceptor moiety of the compound that contributes to LUMO level of the compound, where A2 is nitrogen-containing heteroaryl group, a RuMO group, where M is C, S, P, or As, or a RuSO2 group, or any combination thereof; and
Ru is a mono-, di-, tri, or tetra-substitution, and each substitution is one or more of a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a thiol group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted mono- or dialkylamino group, a substituted or unsubstituted mono- or diarylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxy carbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramide group, a mercapto group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.

### Claim 17 (depends on 15)

The composition of claim 15, wherein ring B is an aryl group.

### Claim 18 (depends on 1)

A light emitting device comprising the thermally activated delayed fluorescent composition of claim 1.

### Claim 19 (depends on 18)

The light emitting device of claim 18, wherein the light emitting device is an organic light emitting diode.

### Claim 20 (depends on 18)

The light emitting device of claim 18, wherein the device comprises a full color display, a photovoltaic device, a luminescent display device or a phosphorescent display device.