Thermally activated delayed fluorescent material based on 9,10-dihydro-9,9-dimethylacridine analogues for prolonging device longevity

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

1. A thermally activated delayed fluorescent compound represented by Formula I, Formula II, Formula III, or Formula IV: ##STR00188## wherein: ##STR00189## represents n acceptor moieties A, where A is a nitrogen-containing heteroaryl group, a R.sup.qMO group, where M is C, S, P, or As, or a R.sup.qSO.sub.2 group, or any combination thereof; and n=1, 2, or 3, such that the compound includes a single acceptor moiety (A.sup.1), two acceptor moieties (A.sup.1 and A.sup.2), or three acceptor moieties (A.sup.1, A.sup.2, and A.sup.3), and wherein each acceptor moiety is substituted with R.sup.q; L.sub.1, and L.sub.2, and L.sub.3 are each independently —CR.sub.2-, —CO—, or —SiR.sub.2-; and R.sup.m, R.sup.n, R.sup.p, and R.sup.q each independently represent mono-, di-, tri, or tetra-substitution, valency permitting; and each R, R.sup.m, R.sup.n, R.sup.p, and R.sup.q independently represents mono-, di-, tri, or tetra-substitution, valency permitting, and each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an —SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof; wherein the alkyl group, haloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, amino group, mono- or dialkylamino group, alkoxy group, aryloxy group, and heteroaryl group is optionally substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, an SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, and a polymeric group; with the proviso that when the compound is represented by Formula III, R.sup.m and R.sup.n are not pyridyl.

2. The compound of claim 1, wherein A is: ##STR00190## ##STR00191## ##STR00192##

3. The compound of claim 2, wherein A is a nitrogen-containing heteroaryl group comprising 1 to 3 nitrogen atoms.

4. The compound of claim 1, wherein A is ##STR00193## where U, U.sup.1, and U.sup.2 each independently represents N or C with the proviso that when U, U.sup.1 and U.sup.2 are present at least one of them is N.

5. The compound of claim 4, wherein A is ##STR00194##

6. The compound of claim 5, wherein the compound is: ##STR00195##

7. The compound of claim 6, wherein the compound is: ##STR00196## or ##STR00197##

8. The compound of claim 6, wherein the compound is: ##STR00198## or ##STR00199##

9. The compound of claim 1, wherein n is 2 and the compound has the structure selected from the group consisting of: ##STR00200## where: R.sup.u represents mono-, di-, tri, or tetra-substitution, valency permitting; and each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an —SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof; wherein the alkyl group, haloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, amino group, mono- or dialkylamino group, alkoxy group, aryloxy group, and heteroaryl group is optionally substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, an SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, and a polymeric group.

10. The compound of claim 9, wherein n=3, and the compound has the structure selected from the group consisting of: ##STR00201## where R.sup.v represents mono-, di-, tri, or tetra-substitution, valency permitting; and each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an —SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof; wherein the alkyl group, haloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, amino group, mono- or dialkylamino group, alkoxy group, aryloxy group, and heteroaryl group is optionally substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, an SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, and a polymeric group.

11. The compound of claim 1, having the structure selected from the group consisting of: ##STR00202## where: L.sub.3 and L.sub.4 are each independently —CR.sub.2-, —CO—, or —SiR.sub.2-; and R.sup.m, R.sup.n, R.sup.s, R.sup.t, each independently represents mono-, di-, tri, or tetra-substitution, valency permitting, and each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an —SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof, where the alkyl group, haloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, amino group, mono- or dialkylamino group, alkoxy group, aryloxy group, and heteroaryl group is optionally substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, an SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, a alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, and a polymeric group.

12. The compound of claim 11, wherein the structure is: ##STR00203## where n=1 and L.sub.1, L.sub.2, L.sub.3, L.sub.4, L.sub.5, and L.sub.6 are each independently —CR.sub.2-, —CO—, or —SiR.sub.2-; and R, R.sub.1, R.sub.2, R.sup.a, R.sup.b, R.sup.e, R.sup.d, R.sup.e, R.sup.f, R.sup.q, R.sup.h, and R.sup.i each independently represents mono-, di-, tri, or tetra-substitution, valency permitting, and each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an —SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof; wherein the alkyl group, haloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, amino group, mono- or dialkylamino group, alkoxy group, aryloxy group, and heteroaryl group is optionally substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, an SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, and a polymeric group.

13. A thermally activated delayed fluorescent compound having a structure selected from the group consisting of: ##STR00204## where: ##STR00205## represents n acceptor moieties A, where A is a nitrogen-containing heteroaryl group, a R.sup.qMO group, where M is C, S, P, or As, or a R.sup.qSO.sub.2 group, or any combination thereof, and n=1, 2, or 3, such that the compound includes a single acceptor moiety (A.sup.1), two acceptor moieties (A.sup.1 and A.sup.2), or three acceptor moieties (A.sup.1, A.sup.2, and A.sup.3), and wherein each acceptor moiety is substituted with R.sup.q; B and B.sup.2 are each independently a substituted electron-deficient aromatic group, L.sub.1 and L.sub.2 are each independently —CR.sub.2-, —CO—, or —SiR.sub.2-; R.sup.m, R.sup.n, R.sup.s, and R.sup.t each independently represents mono-, di-, tri, or tetra-substitution, valency permitting, and each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an —SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof, wherein the alkyl group, haloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, amino group, mono- or dialkylamino group, alkoxy group, aryloxy group, and heteroaryl group is optionally substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, an SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, and a polymeric group.

14. The compound of claim 13, wherein n=2, and the compound is: ##STR00206##

15. The compound of claim 13, wherein B is an aryl group.

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

17. The light emitting device of claim 16, wherein the light emitting device is an organic light emitting diode.

18. The light emitting device of claim 16, wherein the device comprises a full color display, a photovoltaic device, a luminescent display device or a phosphorescent display device.

19. A thermally activated delayed fluorescent compound represented by Formula II, Formula III, or Formula IV: ##STR00207## wherein: ##STR00208## represents n acceptor moieties A, where A is a nitrogen-containing heteroaryl group, a R.sup.qMO group, where M is C, S, P, or As, or a R.sup.qSO.sub.2 group, or any combination thereof; and n=1, 2, or 3, such that the compound includes a single acceptor moiety (A.sup.1), two acceptor moieties (A.sup.1 and A.sup.2), or three acceptor moieties (A.sup.1, A.sup.2, and A.sup.3), and wherein each acceptor moiety is substituted with R.sup.q; L.sub.1, L.sub.2, and L.sub.3 are each independently —CR.sub.2-, —CO—, or —SiR.sub.2-; and R.sup.m, R.sup.n, R.sup.p, and R.sup.q each independently represent mono-, di-, tri, or tetra-substitution, valency permitting; and each R, R.sup.m, R.sup.n, R.sup.p, and R.sup.q independently represents mono-, di-, tri, or tetra-substitution, valency permitting, and each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an —SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof; wherein the alkyl group, haloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, amino group, mono- or dialkylamino group, alkoxy group, aryloxy group, and heteroaryl group is optionally substituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, an SH group, a nitro group, a cyano group, an alkyl group, a haloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a mono- or dialkylamino group, a mono- or diarylamino group, an alkoxy group, an aryloxy group, a heteroaryl group, an alkoxycarbonyl group, an alkylcarbonyloxy 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 sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, and a polymeric group; with the proviso that when the compound is represented by Formula III, R.sup.m and R.sup.n are not pyridyl.

20. The thermally activated delayed fluorescent compound of claim 19, wherein the compound is represented by Formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The thermally activated delayed fluorescent compounds of the present invention provide solutions to short operation time in optical devices. The solution is premised on analogues of 9,10-dihydro-9,9-dimethylacridine compounds. The compounds can improve both the luminescent efficiency and operational stability of a TADF device. Furthermore, the compounds of the present invention may exhibit low degradation during the course of device operation, and therefore facilitate and enhance the longevity of the corresponding TADF device. These and other features of thermally activated delayed fluorescent materials will be described in further detail.

(2) A. Thermally Activated Delayed Fluorescent Compounds

(3) As described herein, a composition may include one or more compounds of the formulas:

(4) ##STR00007##
A.sup.n can independently represent one or more acceptor moieties of the compound, where n is 1 to 3, and contribute to the LUMO level of the compound. In some embodiments, A.sup.n is an electron-deficient aromatic group. Non-limiting examples of A include:

(5) ##STR00008## ##STR00009## ##STR00010##
R.sup.q, R.sup.7, and R.sup.8 can each independently be 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, 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, or a combination thereof. In some embodiments, A is a nitrogen-containing aromatic ring or substituted nitrogen-containing aromatic ring. In a preferred embodiment, A is:

(6) ##STR00011##
where R.sup.q is defined above.

(7) L.sub.1, L.sub.2, and L.sub.3 can be linkage groups, and can include 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. In some embodiments, L.sub.1, L.sub.2 and L.sub.3 can each independently be:

(8) ##STR00012##
where R, R.sub.1 and R.sub.2 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.

(9) R.sup.m, R.sup.n, and R.sup.p 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.

(10) Non-limiting examples of the above structures I-IV include:

(11) ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069##

(12) ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101##
where R.sup.q, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and (R.sup.7).sub.n are each independently 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, 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, or a combination thereof. U, U.sup.1, and U.sup.2 each independently represents N or C of an aromatic ring, with the proviso that when U, U.sup.1 and U.sup.2 present in the same structure, at least one of them is N. V, and V.sup.1 each independently represents NR, O, S, where R can be a alkyl, cycloalkyl, aryl, heteroaryl. In some instances, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and (R.sup.7).sub.n are each independently a hydrogen atom, an alkyl group (e.g., methyl, ethyl or propyl group), or an aromatic (e.g., phenyl) group. In some embodiments, (R.sup.7).sub.n includes two aromatic groups and hydrogen atoms.

(13) In certain embodiments, structures I, II, or III can include two acceptor moieties, and can be represented by the following general structures.

(14) ##STR00102##
where L.sub.1, L.sub.2, R.sup.m, R.sup.n, R.sup.p, R.sup.q, A.sup.1, and A.sup.2 have been previously defined, and R.sup.u can represent 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. Non-limiting examples of the above structures include:

(15) ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, (R.sup.7).sub.n and (R.sup.8).sub.n are as defined above. In some instances, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, (R.sup.7).sub.n and (R.sup.8).sub.n are each independently 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, 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, or a combination thereof. U, U.sup.1, and U.sup.2 each independently represents N or C of an aromatic ring, with the proviso that when U, U.sup.1 and U.sup.2 present in the same structure, at least one of them is N. V, and V.sup.1 each independently represents NR, O, S, wherein R represents alkyl, cycloalkyl, aryl, heteroaryl. In some instances, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, (R.sup.7).sub.n, and (R.sup.8).sub.n are each independently a hydrogen atom, an alkyl group (e.g., methyl, ethyl or propyl group), or an aromatic (e.g., phenyl) group. In some embodiments, (R.sup.7).sub.n and (R.sup.8).sub.n include two aromatic groups with the balance of the substituents being hydrogen atoms.

(16) In certain embodiments, structures I, II, or III can include three acceptor moieties and can be represented by the following general structures.

(17) ##STR00121##
where L.sub.1, L.sub.2, R.sup.m, R.sup.n, R.sup.p, R.sup.q, R.sup.U A.sup.1, A.sup.2, and A.sup.3 have been previously defined, and R.sup.v can represent 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. Non-limiting examples of the above structures VIII, IX, and X include:

(18) ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, (R.sup.7).sub.n, (R.sup.8).sub.n, R.sup.9, and R.sup.10 are as defined above. In some instances, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, (R.sup.7).sub.n, (R.sup.8).sub.n, R.sup.9, and R.sup.10 are each independently 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, 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, or a combination thereof. U, U.sup.1, and U.sup.2 each independently represents N or C of an aromatic ring, with the proviso that when U, U.sup.1 and U.sup.2 present in the same structure, at least one of them is N. V, and V.sup.1 each independently represents NR, O, S, where R can be an alkyl, cycloalkyl, aryl, heteroaryl. In some instances, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, (R.sup.7).sub.n, (R.sup.8).sub.n, R.sup.9, and R.sup.10 are each independently a hydrogen atom, an alkyl group (e.g., methyl, ethyl or propyl group), or an aromatic (e.g., phenyl) group. In some embodiments, (R.sup.7).sub.n and (R.sup.8).sub.n include two aromatic groups with the balance of the substituents being hydrogen atoms.

(19) In some embodiments, the compounds of the present invention can be represented by the following general structures:

(20) ##STR00148##
where L.sub.1, L.sub.2, R.sup.m, R.sup.n, R.sup.p, R.sup.q, and A.sup.n, have been previously defined. B and B.sup.2 can each be a substituted or unsubstituted electron-deficient aromatic group and can in combination with A.sup.n contribute to the LUMO of the level of the compound. R.sup.s and R.sup.t can 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.

(21) Non-limiting examples of structures XI and XII are:

(22) ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, (R.sup.7).sub.n, (R.sup.8).sub.n, R.sup.9, and R.sup.10 are as defined above. In some instances, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 (R.sup.7).sub.n, (R.sup.8).sub.n, R.sup.9, and R.sup.10 are each independently 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, 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, or a combination thereof. U, U.sup.1, and U.sup.2 each independently represents N or C of an aromatic ring, with the proviso that when U, U.sup.1 and U.sup.2 present in the same structure, at least one of them is N. V, and V.sup.1 each independently represents NR, O, S, where R can be an alkyl, cycloalkyl, aryl, heteroaryl. In some instances, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, (R.sup.7).sub.n, (R.sup.8).sub.n, R.sup.9, and R.sup.10 are each independently a hydrogen atom, an alkyl group (e.g., methyl, ethyl, or propyl group), or an aromatic (e.g., phenyl) group.

(23) In some embodiment, each B can include one or more acceptors A.sup.n, and be represented by the following general structures.

(24) ##STR00160##
where L.sub.1, L.sub.2, R.sup.m, R.sup.n, R.sup.p, R.sup.q, R.sup.s, R.sup.t, R.sup.u, A.sup.1, A.sup.2, and B are as previously defined. Non-limiting examples of the above structures XIII and XIV include:

(25) ##STR00161## ##STR00162## ##STR00163##

(26) In some embodiments, the compounds can be represented by the following general structures:

(27) ##STR00164##
where R.sup.m, R.sup.n, R.sup.p, R.sup.q, R.sup.s, R.sup.t, and A.sup.1 are as previously defined, and where L.sub.1, L.sub.2, L.sub.3 and L.sub.4 are linked directly or through a linking atom or group to A.sup.1 and can be:

(28) ##STR00165##
where R, R.sub.1, and R.sub.2 are as previously defined. Non-limiting examples of structures XV, XVI, and XVII include:

(29) ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176##

(30) In some embodiments, the compositions disclosed herein include one or more of the following:

(31) ##STR00177##
where A.sup.1 is as defined above. L.sub.1, L.sub.2, L.sub.3, L.sub.4, L.sub.5, and L.sub.6 can be linkage groups, and can include 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. In some embodiments, L.sub.1, L.sub.2, L.sub.3, L.sub.4, L.sub.5, and L.sub.6 can each independently be:

(32) ##STR00178## where R, R.sub.1 and R.sub.2 are as previously defined.

(33) R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f, R.sup.g, R.sup.h, and R.sup.i can 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.

(34) Non-limiting examples of compounds XVIII, XIX, and XX include:

(35) ##STR00179## ##STR00180## ##STR00181##

(36) Implementations of the present invention may include one or more of the following features. In some cases, for example, the polymeric group includes a polyalkylene, a polyether, or a polyester. In certain cases, for at least one of the compounds, at least one of the following is true: R.sub.a is fused to L.sub.1, R.sub.b is fused to L.sub.2, R is fused to L.sub.3, and R.sub.d is fused to L.sub.4. The composition, or a compound of the composition, may have a neutral charge.

(37) In some embodiments, the thermally activated delayed fluorescent composition (TADF) can be compound shown herein or any mixture thereof. In certain embodiments, the thermally activated delayed fluorescent composition is compound 1, 2, 3, or 4 below, or any mixture thereof.

(38) ##STR00182## ##STR00183##
B. Method of Making Thermally Activated Delayed Fluorescent Compositions

(39) The thermally activated delayed fluorescent compositions can be made using known organic synthetic methodology and exemplified in the Example section. In one non-limiting aspect, the thermally activated delayed fluorescent materials can be prepared using Suzuki-Miyaura reaction methodology. A general synthetic route for the synthesis of the thermally activated delayed fluorescent compositions is shown in reaction scheme (1).

(40) ##STR00184##

(41) The donor portion of the TADF composition can include a leaving group (e.g., halogen (Br, I), or tosylate (OTf). The donor portion can be reacted with a diboride to form donor substituted borylated compound. The donor substituted borylated compound can then be coupled with a mono- or di-halogenated acceptor portion of the TADF composition to form the TADF compound having a donor portion and an acceptor portion. A non-limiting example of making compounds 1-4 are shown in reaction scheme (2), shown below. Aromatic halide 5 can be reacted with a diboride to form borylated compound 6. Borylated compound 6 can then be coupled with a mono- or di-halogenated aromatic compound to form thermally activated delayed fluorescent compounds 1 and 2. In a similar manner, aromatic halide 7 can be reacted with a diboride compound to form borylated compound 8. Borylated compound 6 can then be coupled with a mono- or di-halogenated aromatic compound to form thermally activated delayed fluorescent compounds 3 and 4.

(42) ##STR00185## ##STR00186##
C. Uses of Thermally Activated Delayed Fluorescent Compounds

(43) In some implementations, the compositions disclosed herein or blends thereof are used as host materials for OLED applications, such as full color displays. In one aspect, the compositions disclosed herein can be useful in a wide variety of applications, such as, for example, lighting devices. In a further aspect, one or more of the complexes can be useful as host materials for an organic light emitting display device. In another aspect, the compositions disclosed herein are useful in a variety of applications, for example, as light emitting materials. In a further aspect, the compounds can be useful in organic light emitting diodes (OLEDs), luminescent devices and displays, and other light emitting devices. In another aspect, the compositions disclosed herein can be useful as, for example, host materials for OLEDs, lighting applications, and combinations thereof. In another aspect, the compositions disclosed herein can provide improved efficiency and/or operational lifetimes in lighting devices. In some aspects, the compositions disclosed herein can provide improved efficiency and/or operational lifetimes for organic light emitting devices as compared to conventional materials.

Examples

(44) The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters, which can be changed or modified to yield essentially the same results.

(45) Materials.

(46) The materials used to make compounds 1-4 shown in reaction scheme (2) were obtained from commercial sources or made using known organic methods. Potassium acetate, dioxane, 1,1′-Bis(di-tert-butylphosphino)ferrocene]dichloropalladium(II) ((PdCl.sub.2-(dppf)), dppf, bis(pinacolato)diboron, 2-chloro-4,6-diphenyl-1,3,5-triazine, 2,4-dichloro-6-phenyl-1,3,5-triazine, tetrakis(triphenylphosphine) palladium(0), tetrahydrofuran (THF), potassium carbonate, ethyl acetate, hexane, magnesium sulfate (MgSO.sub.4), and chloroform were obtained from Sigma-Aldrich® (USA).

Synthesis of Compounds 6 and 8

(47) Compounds 5 and 7 were made using general organic transformation methodology. The overall synthetic routes for compounds 5 and 7 are shown in reaction schemes (3) and (4) respectively. The reactant amounts, solvents, temperatures and time can be varied depending on the amount of compounds 5 and 7 produced and are within the general knowledge of one skilled in the art of organic synthesis.

(48) ##STR00187##

(49) Referring to the reaction scheme (1), a mixture of potassium acetate (1.6 mmol), dry dioxane (3.3 mL), PdCl.sub.2-(dppf), 13 mg, 0.016 mmol), dppf (9 mg, 0.016 mmol), bis(pinacolato)diboron (150 mg, 0.6 mmol) and compound 5 or 7 (150 mg, 0.54 mmol) was heated and stirred under argon, at reflux for 2 h. The reaction mixture was diluted with ethyl acetate (100 mL), washed with water (50 mL), dried over magnesium sulfate and concentrated in vacuo to a dark brown oil which was purified by flash column chromatography on florisil using gradient elution (from hexane to 5:95 ethyl acetate-hexane) to yield boronate 6 or 8, respectively (75 mg, 54%) as colorless needles.

Synthesis of Compounds 1, 2, 3, and 4

(50) To a solution of 2-chloro-4,6-diphenyl-1,3,5-triazine or 2,4-dichloro-6-phenyl-1,3,5-triazine (2 mmol), 0.482 g of boronate compound 6 or 8 (2.2 mmol) and 1.16 g of tetrakis(triphenylphosphine) palladium(0) (0.1 mmol) in 10 ml of THF were added dropwise, with stirring, a solution of 0.55 g of potassium carbonate (4 mmol) in 10 mL of water. Subsequently, the mixture was stirred and refluxed for 2 days. The cooled mixture was partitioned between water and ethyl acetate. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Mg.sub.2SO.sub.4, and concentrated in vacuo. Then 100 mL of chloroform was added to it, the brown precipitate formed was collected by filtration, washed with 100 mL of chloroform, dried under vacuum, and the products were obtained. The yield was around 70%.