Tetradentate organic electroluminescent materials and devices
New organometallic complexes having bis- or tris-heteroleptic ligands and large aspect ratio in one direction and their use in OLEDs to enhance the efficiency is disclosed. Such compounds can have a structure of Formula III, where rings A, B, C, and D are ring; L 1 and L 3 each a direct bond or a linking group; n 1 and n 2 are 0 or 1; if n 1 or n 2 is 1, then L 2 or L 4 is a direct bond or a linking group, and if n 1 or n 2 is 0, L 2 or L 4 is not present; Q 1 , Q 2 , Q 3 and Q 4 are a direct bond or oxygen; ring A is trans to ring D, ring B is trans to ring C in a square-planar coordination configuration; M 2 is Pt, and the compound comprises at least one Pt-carbene bond.
1. A compound having a formula of Formula III,
wherein rings A, B, C, and D are each a 5 or 6-membered carbocyclic or heterocyclic ring;
wherein L 1 and L 3 are each independently selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO 2 , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof;
wherein n 1 and n 2 each independently is 0 or 1;
wherein, if n 1 or n 2 is 1, then L 2 or L 4 is selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO 2 , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; and
wherein, if n 1 or n 2 is 0, L 2 or L 4 is not present;
Q 1 , Q 2 , Q 3 and Q 4 are each independently selected from the group consisting of direct bond and oxygen;
wherein Z 1 , Z 2 , Z 3 , and Z 4 are each independently carbon or nitrogen;
when any of Z 1 , Z 2 , Z 3 and Z 4 is nitrogen, the Q 1 , Q 2 , Q 3 and Q 4 attached thereto is a direct bond;
ring A is trans to ring D, ring B is trans to ring C in a square-planar coordination configuration;
wherein R 1 , R 2 , R 3 , and R 4 each represents mono to the maximum possible number of substitution, or no substitution;
wherein M 2 is Pt, and the compound comprises at least one Pt-carbene bond;
wherein a fourth distance is the distance between the atom in R 1 that is the farthest away from M 2 to the atom in R 4 that is the farthest away from M 2 ;
wherein a fifth distance is the distance between the atom in R 2 that is the farthest away from M 2 to the atom in R 3 that is the farthest away from M 2 ;
wherein the fourth distance is longer than the fifth distance by at least 1.5 Å;
wherein R, R′, R 1 , R 2 , R 3 , and R 4 are each 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 two substituents among R, R′, R 1 , R 2 , R 3 , and R 4 are optionally joined or fused into a ring; and
wherein at least one of the following is true:
(i) at least one of L 1 to L 3 is a C—C direct bond;
(ii) each of Q 1 to Q 4 is a direct bond; or
(iii) at least two of Q 1 to Q 4 are O.
2. The compound of claim 1 , wherein rings A, B, C, and D are each independently selected from the group consisting of phenyl, pyridine, and imidazole.
3. The compound of claim 1 , wherein rings A and C are phenyl, and rings B and D are selected from the group consisting of pyridine, pyrimidine, imidazole, and pyrazole.
4. The compound of claim 1 , wherein rings B and D are selected from the group consisting of pyridine, pyrimidine, imidazole, and pyrazole.
5. The compound of claim 1 , wherein R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, silyl, aryl, heteroaryl, and combinations thereof.
6. The compound of claim 1 , wherein the fourth distance is longer than the fifth distance by at least 4.3 Å.
7. The compound of claim 1 , wherein at least one of the rings A, B, C, or D is fused by another 5- or 6-membered ring.
8. The compound of claim 1 , wherein the bidentate ligands A-B and C-D are each independently selected from the group consisting of:
wherein X 1 to X 13 are each independently selected from the group consisting of carbon and nitrogen;
wherein X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C—O, S—O, SO 2 , CR′R″, SiR′R″, and GeR′R″;
wherein R′ and R″ are optionally fused or joined to form a ring;
wherein R a , R b , R c , and R c each represents from mono substitution to the maximum possible number of substitution, or no substitution;
wherein R′, R″, R a , R b , R c , and R d are each 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; and
wherein any two substitutents among R a , R b , R c , and R d are optionally fused or joined to form a ring.
9. The compound of claim 8 , wherein the bidentate ligands A-B and C-D are each independently selected from the group consisting of:
10. The compound of claim 1 , wherein each of Q 1 , Q 2 , Q 3 , and Q 4 is a direct bond.
11. The compound of claim 1 , wherein two of Z 1 , Z 2 , Z 3 , and Z 4 are carbon atoms, and the remaining two of Z 1 , Z 2 , Z 3 , and Z 4 are nitrogen atoms;
wherein three of Z 1 , Z 2 , Z 3 , and Z 4 are carbon atoms, and the remaining one of Z 1 , Z 2 , Z 3 , and Z 4 is a nitrogen atom; or
wherein each of Z 1 , Z 2 , Z 3 , and Z 4 are carbon atoms.
12. The compound of claim 1 , wherein the compound is selected from the group consisting of:
13. The compound of claim 1 , wherein the compound is selected from the group consisting of:
wherein R 5 , R 6 , R 7 , R 2′ , and R 3′ each represents mono to the maximum possible number of substitution, or no substitution;
wherein R 5 , R 6 , R 7 , R 2′ , and R 3′ are each 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; and
wherein any two substituents among R, R′, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are optionally joined or fused into a ring.
14. The compound of claim 13 , wherein at least one R 1 and at least one R 4 is selected from the group consisting of:
15. An organic light-emitting device (OLED) comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound having a formula of Formula III,
wherein rings A, B, C, and D are each a 5 or 6-membered carbocyclic or heterocyclic ring;
wherein L 1 and L 3 are each independently selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO 2 , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof;
wherein n 1 and n 2 each independently is 0 or 1;
wherein, if n 1 or n 2 is 1, then L 2 or L 4 is selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO 2 , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; and
wherein, if n 1 or n 2 is 0, L 2 or L 4 is not present;
Q 1 , Q 2 , Q 3 and Q 4 are each independently selected from the group consisting of direct bond and oxygen;
wherein Z 1 , Z 2 , Z 3 , and Z 4 are each independently carbon or nitrogen;
when any of Z 1 , Z 2 , Z 3 and Z 4 is nitrogen, the Q 1 , Q 2 , Q 3 and Q 4 attached thereto is a direct bond;
ring A is trans to ring D, ring B is trans to ring C in a square-planar coordination configuration;
wherein R 1 , R 2 , R 3 , and R 4 each represents mono to the maximum possible number of substitution, or no substitution;
wherein M 2 is Pt, and the compound comprises at least one Pt-carbene bond;
wherein a fourth distance is the distance between the atom in R 1 that is the farthest away from M 2 to the atom in R 4 that is the farthest away from M 2 ;
wherein a fifth distance is the distance between the atom in R 2 that is the farthest away from M 2 to the atom in R 3 that is the farthest away from M 2 ;
wherein the fourth distance is longer than the fifth distance by at least 1.5 Å;
wherein R, R′, R 1 , R 2 , R 3 , and R 4 are each 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 two substituents among R, R′, R 1 , R 2 , R 3 , and R 4 are optionally joined or fused into a ring; and
wherein at least one of the following is true:
(i) at least one of L 1 to L 3 is a C—C direct bond;
(ii) each of Q 1 to Q 4 is a direct bond; or
(iii) at least two of Q 1 to Q 4 are O.
16. A consumer product comprising an organic light-emitting device comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound having a formula of Formula III,
wherein rings A, B, C, and D are each a 5 or 6-membered carbocyclic or heterocyclic ring;
wherein L 1 and L 3 are each independently selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO 2 , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof;
wherein n 1 and n 2 each independently is 0 or 1;
wherein, if n 1 or n 2 is 1, then L 2 or L 4 is selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO 2 , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; and
wherein, if n 1 or n 2 is 0, L 2 or L 4 is not present;
Q 1 , Q 2 , Q 3 and Q 4 are each independently selected from the group consisting of direct bond and oxygen;
wherein Z 1 , Z 2 , Z 3 , and Z 4 are each independently carbon or nitrogen;
when any of Z 1 , Z 2 , Z 3 and Z 4 is nitrogen, the Q 1 , Q 2 , Q 3 and Q 4 attached thereto is a direct bond;
ring A is trans to ring D, ring B is trans to ring C in a square-planar coordination configuration;
wherein R 1 , R 2 , R 3 , and R 4 each represents mono to the maximum possible number of substitution, or no substitution;
wherein M 2 is Pt, and the compound comprises at least one Pt-carbene bond;
wherein a fourth distance is the distance between the atom in R 1 that is the farthest away from M 2 to the atom in R 4 that is the farthest away from M 2 ;
wherein a fifth distance is the distance between the atom in R 2 that is the farthest away from M 2 to the atom in R 3 that is the farthest away from M 2 ;
wherein the fourth distance is longer than the fifth distance by at least 1.5 Å;
wherein R, R′, R 1 , R 2 , R 3 , and R 4 are each 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 two substituents among R, R′, R 1 , R 2 , R 3 , and R 4 are optionally joined or fused into a ring; and
wherein at least one of the following is true:
(i) at least one of L 1 to L 3 is a C—C direct bond;
(ii) each of Q 1 to Q 4 is a direct bond; or
(iii) at least two of Q 1 to Q 4 are O.
17. A formulation comprising a compound of claim 1 .
18. The compound of claim 1 , wherein at least one of L 1 to L 3 is a C—C direct bond.
19. The compound of claim 1 , wherein at least two of Q 1 to Q 4 are O.
20. The compound of claim 1 , wherein the compound is