Organic electroluminescent materials and devices
A compound having a formula M(L A ) x (L B ) y (L C ) z , where ligand L A is ligand L B is and ligand L C is is disclosed. In formula M(L A ) x (L B ) y (L C ) z , M is a metal having an atomic number greater than 40; x is 1 or 2; y and z are independently 0, 1, or 2; x+y+z is the oxidation state of the metal M; A 1 -A 8 are carbon or nitrogen; ring B is bonded to ring A through a C—C bond; M is bonded to ring A through a M-C bond; X is O, S, Se, CRR′, or NR 1 ; rings C and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; at least one R 4 is a five-membered or six-membered heterocyclic ring which can be further substituted by R E ; each R substituent is independently selected from the several substituents; and any adjacent R substitutents are optionally joined to form a ring.
1 . A compound having a formula M(L A ) x (L B ) y (L C ) z :
wherein the ligand L A is
wherein the ligand L B is
wherein the ligand L C is
wherein M is a metal having an atomic number greater than 40;
wherein x is 1, or 2;
wherein y is 0, 1, or 2;
wherein z is 0, 1, or 2;
wherein x+y+z is the oxidation state of the metal M;
wherein A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , and A 8 are carbon or nitrogen;
wherein ring B is bonded to ring A through a C—C bond;
wherein M is bonded to ring A through a M-C bond;
wherein X is selected from the group consisting of O, S, Se, CRR′, and NR 1 ;
wherein rings C and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring;
wherein R 3 represents mono, or di-substitution, or no substitution;
wherein R 2 , R C , and R D each independently represent mono, di, tri, or tetra-substitution, or no substitution;
wherein R 4 represents mono, di, tri, or tetra-substitution;
wherein at least one R 4 is a five-membered or six-membered heterocyclic ring which can be further substituted by R E ;
wherein R E represents mono, di, tri, or tetra-substitutions, or no substitutions;
wherein each of R, R′, R 1 , R 2 , R 3 , R 4 , R C , R D , R X , R Y , R Z and R E are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any adjacent substituents of R, R′, R X , R Y , and R Z are optionally joined to form a ring; and any two adjacent R 1 , R 2 , R 3 , R 4 , R C , R D , and R E are optionally joined to form an aromatic ring; and
wherein at least one of the following is true:
(i) one of A 2 , A 3 , or A 4 is bonded to ring B, and the R 3 bonded to A 1 is selected from the group consisting of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, partially or fully deuterated variants thereof, and combinations thereof;
(ii) at least one of A 5 to A 8 is N;
(iii) R 4 is a 5-membered or 6-membered heterocycloalkyl ring; or
(iv) A 5 is N and the R 2 bonded to A 6 is selected from the group consisting of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, partially or fully deuterated variants thereof, and combinations thereof.
2 . The compound of claim 1 , wherein M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu.
3 . The compound of claim 1 , wherein the compound has the formula M(L A ) 2 (L C ), the formula M(L A ) 2 (L B ), or the formula M(L A )(L B ) 2 .
4 . The compound of claim 1 , wherein A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , and A 8 are carbon.
5 . The compound of claim 1 , wherein one of A 5 , A 6 , A 7 , or A 8 is nitrogen.
6 . The compound of claim 1 , wherein at least one R 4 is a five-membered or six-membered aromatic heterocyclic ring.
7 . The compound of claim 1 , wherein at least one R 4 is a five-membered or six-membered heterocycloalkyl ring, which can be further substituted by R E .
8 . The compound of claim 1 , wherein each of R, R′, R 1 , R 2 , R 3 , R 4 , R C , R D , and R E is independently selected from group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aryl, heteroaryl, nitrile, and combinations thereof.
9 . The compound of claim 1 , wherein each of R 2 , R 3 , R 4 , R C , R D , and R E is independently selected from group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aryl, heteroaryl, nitrile, and combinations thereof.
10 . The compound of claim 1 , wherein one of A 2 , A 3 , or A 4 is bonded to ring B, and the R 3 bonded to A 1 is selected from the group consisting of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, partially or fully deuterated variants thereof, and combinations thereof.
11 . The compound of claim 1 , wherein L A is selected from the group consisting of
12 . The compound of claim 1 , wherein L B is selected from the group consisting of:
13 . The compound of claim 1 , where L C is selected from the group consisting of:
14 . The compound of claim 1 , wherein L A is selected from the group consisting of:
L A9 through L A16 , each represented
by the formula:
wherein in L A9 : R 1 = R A1 , R 2 = R B1 ,
in L A10 : R 1 = R A2 , R 2 = R B1 ,
in L A11 : R 1 = R A3 , R 2 = R B1 ,
in L A12 : R 1 = R A4 , R 2 = R B1 ,
in L A13 : R 1 = R A1 , R 2 = R B2 ,
in L A14 : R 1 = R A2 , R 2 = R B2 ,
in L A15 : R 1 = R A3 , R 2 = R B2 , and
in L A16 : R 1 = R A4 , R 2 = R B2 ,
L A49 through L A56 , each represented
by the formula:
wherein in L A49 : R 1 = R A1 , R 2 = R B1 ,
in L A50 : R 1 = R A2 , R 2 = R B1 ,
in L A51 : R 1 = R A3 , R 2 = R B1 ,
in L A52 : R 1 = R A4 , R 2 = R B1 ,
in L A53 : R 1 = R A1 , R 2 = R B2 ,
in L A54 : R 1 = R A2 , R 2 = R B2 ,
in L A55 : R 1 = R A3 , R 2 = R B2 , and
in L A56 : R 1 = R A4 , R 2 = R B2 ,
L A57 through L A64 , each represented
by the formula:
where in L A57 : R 1 = R A1 , R 2 = R B1 ,
in L A58 : R 1 = R A2 , R 2 = R B1 ,
in L A59 : R1 = R A3 , R 2 = R B1 ,
in L A60 : R 1 = R A4 , R 2 = R B1 ,
in L A61 : R 1 = R A1 , R 2 = R B2 ,
in L A62 : R 1 = R A2 , R 2 = R B2 ,
in L A63 : R 1 = R A3 , R 2 = R B2 , and
in L A64 : R 1 = R A4 , R 2 = R B2 ,
L A65 through L A72 , each represented
by the formula:
wherein in L A65 : R 1 = R A1 , R 2 = R B1 ,
in L A66 : R 1 = R A2 , R 2 = R B1 ,
in L A67 : R1 = R A3 , R 2 = R B1 ,
in L A68 : R 1 = R A4 , R 2 = R B1 ,
in L A69 : R 1 = R A1 , R 2 = R B2 ,
in L A70 : R 1 = R A2 , r 2 = R B2 ,
in L A71 : R 1 = R A3 , R 2 = R B2 , and
in L A72 : R 1 = R A4 , R 2 = R B2 ,
L A73 through L A80 , each represented
by the formula:
wherein in L A73 : R 1 = R A1 , R 2 = R B1 ,
in L A74 : R 1 = R A2 , R 2 = R B1 ,
in L A75 : R 1 = R A3 , R 2 = R B1 ,
in L A76 : R 1 = R A4 , R 2 = R B1 ,
in L A77 : R 1 = R A1 , R 2 = R B2 ,
in L A78 : R 1 = R A2 , R 2 = R B2 ,
in L A79 : R 1 = R A3 , R 2 = R B2 , and
in L A80 : R 1 = R A4 , R 2 = R B2 ,
L A101 through L A104 , each represented
by the formula:
wherein in L A101 : X = O, R 2 = R B1 ,
in L A102 : X = O, R 2 = R B2 ,
in L A103 : X = S, R 2 = R B1 , and
in L A104 : X = S, R 2 = R B2 ,
L A129 through L A134 , each represented
by the formula:
wherein in L A129 : X = O, R 2 = R B1 ,
in L A130 : X = O, R 2 = R B2 ,
in L A131 : X = S, R 2 = R B1 ,
in L A132 : X = S, R 2 = R B2 ,
in L A133 : X = C(CH 3 ) 2 , R 2 = R B1 , and
in L A134 : X = C(CH 3 ) 2 ), R 2 = R B2 ,
L A135 through L A140 , each represented
by the formula:
wherein in L A135 : X = O, R 2 = R B1 ,
in L A136 : X = O, R 2 = R B2 ,
in L A137 : X = S, R 2 = R B1 ,
in L A138 : X = S, R 2 = R B2 ,
in L A139 : X = C(CH 3 ) 2 , R 2 = R B1 , and
in L A140 : X = C(CH 3 ) 2 , R 2 = R B2 ,
L A141 through L A146 , each represented
by the formula:
wherein in L A141 : X = O, R 2 = R B1 ,
in L A142 : X = O, R 2 = R B2 ,
in L A143 : X = S, R 2 = R B1 ,
in L A144 : X = S, R 2 = R B2 ,
in L A145 : X = C(CH 3 ) 2 , R 2 = R B1 , and
in L A146 : X = C(CH 3 ) 2 , R 2 = R B2 ,
L A147 through L A152 each represented
by the formula:
wherein in L A147 : R 1 = R A1 , R 2 = R B1 ,
in L A148 : R 1 = R A2 , R 2 = R B1 ,
in L A149 : R 1 = R A1 , R 2 = R B2 ,
in L A150 : R 1 = R A2 , R 2 = R B2 ,
in L A151 : X = C(CH 3 ) 2 , R 2 = R B1 , and
in L A152 : X = C(CH 3 ) 2 , R 2 = R B2 ,
L A153 through L A158 , each represented
by the formula:
wherein in L A153 : R 1 = R A1 , R 2 = R B1 ,
in L A154 : R 1 = R A2 , R 2 = R B1 ,
in L A155 : R 1 = R A1 , R 2 = R B2 ,
in L A156 : R 1 = R A2 , R 2 = R B2 ,
in L A157 : X = C(CH 3 ) 2 , R 2 = R B1 , and
in L A158 : X = C(CH 3 ) 2 , R 2 = R B2 ,
L A171 through L A176 , each represented
by the formula:
wherein in L A171 : X = O, R 2 = R B1 ,
in L A172 : X = O, R 2 = R B2 ,
in L A173 : X = S, R 2 = R B1 ,
in L A174 : X = S, R 2 = R B2 ,
in L A175 : X = C(CH 3 ) 2 , R 2 = R B1 , and
in L A176 : X = C(CH 3 ) 2 , R 2 = R B2 , and
L A177 through L A182 , each represented
by the formula:
wherein in L A177 : X = O, R 2 = R B1 ,
in L A178 : X = O, R 2 = R B2 ,
in L A179 : X = S, R 2 = R B1 ,
in L A180 : X = S, R 2 = R B2 ,
in L A181 : X = C(CH 3 ) 2 , R 2 = R B1 , and
in L A182 : X = C(CH 3 ) 2 , R 2 = R B2 .;
wherein
R A1 to R A4 have the following structures:
and
R B1 and R B2 have the following structures
15 . The compound of claim 1 , wherein one of A 2 , A 3 , or A 4 is bonded to ring B and the R 3 bonded to A 1 is alkyl, cycloalkyl, aryl, heteroaryl, partially or fully deuterated variants thereof, and combinations thereon.
16 . The compound of claim 1 , wherein A 5 is N and the R 2 bonded to A 6 is alkyl or partially or fully deuterated alkyl.
17 . The compound of claim 1 , wherein A 5 is N and the R 2 bonded to A 6 is CD 3 .
18 . A device comprising one or more organic light emitting devices, at least one of the one or more organic light emitting devices comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound having a formula M(L A ) x (L B ) y (L C ) z :
wherein the ligand L A is
wherein the ligand L B is
wherein the ligand L C is
wherein M is a metal having an atomic number greater than 40;
wherein x is 1, or 2;
wherein y is 0, 1, or 2;
wherein z is 0, 1, or 2;
wherein x+y+z is the oxidation state of the metal M;
wherein A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , and A 8 are carbon or nitrogen;
wherein ring B is bonded to ring A through a C—C bond;
wherein M is bonded to ring A through a M-C bond;
wherein X is selected from the group consisting of O, S, Se, CRR′, and NR 1 ;
wherein rings C and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring;
wherein R 3 represents mono, or di-substitution, or no substitution;
wherein R 2 , R C , and R D each independently represent mono, di, tri, or tetra-substitution, or no substitution;
wherein R 4 represents mono, di, tri, or tetra-substitution;
wherein at least one R 4 is a five-membered or six-membered heterocyclic ring which can be further substituted by R E ;
wherein R E represents mono, di, tri, or tetra-substitutions, or no substitutions;
wherein each of R, R′, R 1 , R 2 , R 3 , R 4 , R C , R D , R X , R Y , R Z and R E are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any adjacent substituents of R, R′, R X , R Y , and R Z are optionally joined to form a ring; and any two adjacent R 1 , R 2 , R 3 , R 4 , R C , R D , and R E are optionally joined to form an aromatic ring; and
wherein at least one of the following is true:
(i) one of A 2 , A 3 , or A 4 is bonded to ring B, and the R 3 bonded to A 1 is selected from the group consisting of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, partially or fully deuterated variants thereof, and combinations thereof;
(ii) at least one of A 5 to A 8 is N;
(iii) R 4 is a 5-membered or 6-membered heterocycloalkyl ring; or
(iv) A 5 is N and the R 2 bonded to A 6 is selected from the group consisting of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, partially or fully deuterated variants thereof, and combinations thereof.
19 . The device of claim 18 , wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
20 . A formulation comprising a compound having a formula M(L A ) x (L B ) y (L C ) 2 :
wherein the ligand L A is
wherein the ligand L B is
wherein the ligand L C is
wherein M is a metal having an atomic number greater than 40;
wherein x is 1, or 2;
wherein y is 0, 1, or 2;
wherein z is 0, 1, or 2;
wherein x+y+z is the oxidation state of the metal M;
wherein A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , and A 8 are carbon or nitrogen;
wherein ring B is bonded to ring A through a C—C bond;
wherein M is bonded to ring A through a M-C bond;
wherein X is selected from the group consisting of O, S, Se, CRR′, and NR 1 ;
wherein rings C and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring;
wherein R 3 represents mono, or di-substitution, or no substitution;
wherein R 2 , R C , and R D each independently represent mono, di, tri, or tetra-substitution, or no substitution;
wherein R 4 represents mono, di, tri, or tetra-substitution;
wherein at least one R 4 is a five-membered or six-membered heterocyclic ring which can be further substituted by R E ;
wherein R E represents mono, di, tri, or tetra-substitutions, or no substitutions;
wherein each of R, R′, R 1 , R 2 , R 3 , R 4 , R C , R D , R X , R Y , R Z and R E are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any adjacent substituents of R, R′, R X , R Y , and R Z are optionally joined to form a ring; and any two adjacent R 1 , R 2 , R 3 , R 4 , R C , R D , and R E are optionally joined to form an aromatic ring; and
wherein at least one of the following is true:
(i) one of A 2 , A 3 , or A 4 is bonded to ring B, and the R 3 bonded to A 1 is selected from the group consisting of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, partially or fully deuterated variants thereof, and combinations thereof;
(ii) at least one of A 5 to A 8 is N;
(iii) R 4 is a 5-membered or 6 -membered heterocycloalkyl ring; or
(iv) A 5 is N and the R 2 bonded to A 6 is selected from the group consisting of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, partially or fully deuterated variants thereof, and combinations thereof.