Organic electroluminescent materials and devices

1 . A metal coordination complex having a formula of M(L A ) p (L B ) q (L C ) r , wherein ligand L A comprises a structure of the following Formula I

wherein:

p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M;

Q is C or Si;

m and n are each independently 1 or 2;

each independently represents a single bond or a double bond in a Lewis structural drawing;

each one of ring A and ring B independently comprises exactly one double bond in at least one Lewis structural drawing;

R A and R B each independently represent di to the maximum allowable substitution;

each R A and R B is independently a hydrogen, or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, germyl, boryl, selenyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

at least one pair of adjacent substituents R A are joined to form a 5- or 6-membered aromatic or heteroaromatic ring, referred to as ring A 1′ ;

at least one pair of adjacent substituents R B are joined to form a 5- or 6-membered aromatic or heteroaromatic ring, referred to as ring B 1′ ;

wherein (i) at least one of R A or R B comprises a ring system, which can be aromatic or heteroaromatic, with 3 to 30 ring atoms, wherein one ring of the ring system is bonded to the metal, (ii) ring A 1′ or ring B 1′ is bonded to the metal M, or (iii) both condition (i) and condition (ii);

the metal M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;

L B and L C are each bidentate ligands; and

with the provisos that

(I) if ring A 1′ is a benzene ring and two substituents R A are joined to form a second benzene ring A 1″ fused to ring A, then at least one of the following is true: (a) ring A 1′ or ring A 1″ is coordinated to the metal M, (b) the metal M is Pt or Pd, p is 1, q is 1, r is 0, and L A and L B are joined to form a tetradentate ligand, or (c) ring A 1′ and ring A 1″ are fused together; and

(II) if ring B 1′ is a benzene ring and two substituents R B are joined to form a second benzene ring B 1″ fused to ring B, then at least one of the following is true (a) ring B 1′ or ring B 1″ is coordinated to the metal M, (b) the metal M is Pt or Pd, p is 1, q is 1, r is 0, and L A and L B are joined to form a tetradentate ligand, or (c) ring B 1′ and ring B 1″ are fused together.

2 . The compound of claim 1 , wherein each R A and R B is independently a hydrogen, or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

3 . The compound of claim 1 , wherein ring A 1′ is a benzene ring, two substituents R A are joined to form a second benzene ring fused to ring A, and ring A 1′ and the second benzene ring are fused together; or ring B 1′ is a benzene ring, two substituents R B are joined to form a second benzene ring fused to ring B, and ring B 1′ and the second benzene ring are fused together.

4 . The compound of claim 1 , wherein the one of ring A 1′ or ring B 1′ bonded to the metal M is a ring selected from the group consisting of benzene, pyridine, pyrimidine, pyrazine, triazine, imidazole, benzimidazole, quinoline, isoqinoline, naphthalene, and pyrazole.

5 . The compound of claim 1 , wherein at least one of R A or R B comprises the one ring bonded to the metal M.

6 . The compound of claim 5 , wherein the one ring is joined to ring A 1′ or ring B 1′ , respectively, by a direct bond or an organic linker.

7 . The compound of claim 1 , wherein the compound has the Formula II:

where:

at least one of L A ,

is selected from the group consisting of

wherein:

each of k, l, k′, l′, m′, and n′ is independently 0, 1, or 2;

m′+n′ is 2 or 3, k+l is 2 or 3, and k′+l′ is 1 or 2;

Z′, Z″, Z 1 , Z 2 , Z 3 , and Z 4 are independently selected from group consisting of C and N

when present, each of ring S, ring T, ring U, ring U 1 , and ring U 2 is independently an aromatic or heteroaromatic ring or ring system with 3 to 30 ring atoms;

when present, each of Ring S, ring T, ring U, ring U 1 , and ring U 2 , can be unsubstituted or substituted with up to the maximum possible substituents R S , R T , R U , R U1 , and R U2 , respectively;

each of R S , R T , R U , R U1 , and R U2 is independently selected hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

any pair of substituents R A , R B , R T , R U , R U1 , and R U2 can be joined or fused to form a ring,

M 1 is Pd or Pt;

the dashed lines represent bonds to metal M 1 ;

each of ring A 1 and ring A 2 is independently an aromatic or heteroaromatic ring or ring system having 3 to 10 ring atoms;

ring C is a C 1 to C 15 aromatic or heteroaromatic ring or ring system;

K 3 and K 4 are each independently selected from the group consisting of a direct bond, O, and S, wherein at least one of K 3 and K 4 is a direct bond;

L 1 , L 2 , L 3 , and L 4 are each independently selected from the group consisting of a single bond, absent a bond, O, S, CR′R″, SiR′R″, BR′, and NR′, wherein at least one of L 1 and L 2 is present, wherein each R′ and R″ is independently a hydrogen, or a substituent selected from the group consisting of deuterium, halogen, alkyl cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

at least three of L 1 to L 4 are present;

R C , R D , R E and R F each independently represent zero, mono, or up to a maximum allowed substitution to its associated ring;

each of R C , R D , R E and R F is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof;

any two substituents can be joined or fused together to form a ring.

8 . The compound of claim 7 , wherein the compound is selected from the group consisting of:

wherein:

R x and R y are each selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;

R G for each occurrence is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof;

Z 1 , Z 2 , Z 3 , and Z 4 are independently selected from C or N;

Rp is selected from the group consisting of BR, BRR′, NR, PR, P(O)R, O, S, Se, C═O, C═S, C=Se, C=NR, C=CRR′, S═O, SO 2 , CR, CRR′, SiRR′, GeRR′, alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof;

L 1 and L 4 are independently selected from the group consisting of a single bond, absent a bond, O, S, CR′R″, SiR′R″, BR′, and NR′;

R A1 , R B1 , R C , R D , R E and R F each independently represents zero, mono, or up to a maximum allowed substitution to its associated ring;

each of R, R′, R A1 , R B1 , R C , R D , R E and R F is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof;

any two substituents can be joined or fused together to form a ring;

X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 are each independently selected from CR q and N, wherein each R q is independently hydrogen or a substituent selected from the group consisting of the general substituents; and

ring C is a C 1 to C 15 aromatic or heteroaromatic ring or ring system.

9 . The compound of claim 8 , wherein the compound has a structure of Formula III:

wherein at least one of R* 1 , R* 2 , R* 3 , R* 4 or R* 5 comprises a structure of the Formula I, and

each R* 1 , R* 2 , R* 3 , R* 4 and R* 5 is independently a hydrogen, or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

10 . The compound of claim 9 , wherein two adjacent R* 1 , R* 2 , R* 3 , R* 4 are joined or fused together to form ring A 1′ .

11 . The compound of claim 9 , wherein two adjacent R* 1 , R* 2 , R* 3 , R* 4 are joined or fused together to form ring A.

12 . The compound of claim 9 , wherein two adjacent R* 3 are joined or fused together to form ring A.

13 . The compound of claim 9 , wherein one R* 1 , R* 2 , R* 3 , R* 4 , and R* 5 comprises a structure of Formula I.

14 . The compound of claim 9 , wherein R* 5 comprises the structure of Formula I.

15 . The compound of claim 9 , wherein R* 5 comprises an aryl moiety substituted by a structure of Formula I.

16 . The compound of claim 7 , wherein the compound is selected from the group consisting of:

17 . An organic light emitting device (OLED) comprising:

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a metal coordination complex comprising having a formula of M(L A ) p (L B ) q (L C ), wherein ligand L A comprises a structure of the following Formula I

wherein:

p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M;

Q is C or Si;

m and n are each independently 1 or 2;

each independently represents a single bond or a double bond in a Lewis structural drawing;

each one of ring A and ring B independently comprises exactly one double bond in at least one Lewis structural drawing;

R A and R B each independently represent di to the maximum allowable substitution;

each R A and R B is independently a hydrogen, or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, germyl, boryl, selenyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

at least one pair of adjacent substituents R A are joined to form a 5- or 6-membered aromatic or heteroaromatic ring, referred to as ring A 1′ ;

at least one pair of adjacent substituents R B are joined to form a 5- or 6-membered aromatic or heteroaromatic ring, referred to as ring B 1′ ;

wherein (i) at least one of R A or R B comprises a ring system, which can be aromatic or heteroaromatic, with 3 to 30 ring atoms, wherein one ring of the ring system is bonded to the metal, (ii) ring A 1′ or ring B 1′ is bonded to the metal M, or (iii) both condition (i) and condition (ii);

the metal M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;

L B and L C are each bidentate ligands; and

with the provisos that

(I) if ring A 1′ is a benzene ring and two substituents R A are joined to form a second benzene ring A 1″ fused to ring A, then at least one of the following is true: (a) ring A 1′ or ring A 1″ is coordinated to the metal M, (b) the metal M is Pt or Pd, p is 1, q is 1, r is 0, and L A and L B are joined to form a tetradentate ligand, or (c) ring A 1′ and ring A 1″ are fused together; and

(II) if ring B 1′ is a benzene ring and two substituents R B are joined to form a second benzene ring B 1″ fused to ring B, then at least one of the following is true (a) ring B 1′ or ring B 1″ is coordinated to the metal M, (b) the metal M is Pt or Pd, p is 1, q is 1, r is 0, and L A and L B are joined to form a tetradentate ligand, or (c) ring B 1′ and ring B 1″ are fused together.

18 . The OLED of claim 17 , wherein the organic layer further comprises a host, wherein host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

19 . A consumer product comprising an organic light-emitting device (OLED) comprising:

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a metal coordination complex having a formula of M(L A ) p (L B ) q (L C ) r , wherein ligand L A comprises a structure of the following Formula I

wherein:

p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M;

Q is C or Si;

m and n are each independently 1 or 2;

each independently represents a single bond or a double bond in a Lewis structural drawing;

each one of ring A and ring B independently comprises exactly one double bond in at least one Lewis structural drawing;

R A and R B each independently represent di to the maximum allowable substitution;

each R A and R B is independently a hydrogen, or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, germyl, boryl, selenyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

at least one pair of adjacent substituents R A are joined to form a 5- or 6-membered aromatic or heteroaromatic ring, referred to as ring A 1′ ;

at least one pair of adjacent substituents R B are joined to form a 5- or 6-membered aromatic or heteroaromatic ring, referred to as ring B 1′ ;

wherein (i) at least one of R A or R B comprises a ring system, which can be aromatic or heteroaromatic, with 3 to 30 ring atoms, wherein one ring of the ring system is bonded to the metal, (ii) ring A 1′ or ring B 1′ is bonded to the metal M, or (iii) both condition (i) and condition (ii);

the metal M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;

L B and L C are each bidentate ligands; and

with the provisos that

(I) if ring A 1′ is a benzene ring and two substituents R A are joined to form a second benzene ring A 1″ fused to ring A, then at least one of the following is true: (a) ring A 1′ or ring A 1″ is coordinated to the metal M, (b) the metal M is Pt or Pd, p is 1, q is 1, r is 0, and L A and L B are joined to form a tetradentate ligand, or (c) ring A 1′ and ring A 1″ are fused together; and

(II) if ring B 1′ is a benzene ring and two substituents R B are joined to form a second benzene ring B 1″ fused to ring B, then at least one of the following is true (a) ring B 1′ or ring B 1″ is coordinated to the metal M, (b) the metal M is Pt or Pd, p is 1, q is 1, r is 0, and L A and L B are joined to form a tetradentate ligand, or (c) ring B 1′ and ring B 1″ are fused together.

20 . The compound of claim 1 , wherein metal M is Pt or Pd, p is 1, q is 1, r is 0, and L A and L B are connected to form a tetradentate ligand.