Organic electroluminescent materials and devices
A compound having a structure of Formula I, is provided. In Formula I, each of moieties B, C, and D is a ring or multicyclic ring system; each of X 1 , X 2 , X 3 , X 4 , X 5 , Y 1 , Z 1 , Z 2 , Z 3 , Z 4 , and Z 5 is C or N; each of K 1 , K 2 , and K 3 is a direct bond, O, or S; L 1 and L 2 are independently direct bonds or bivalent linking groups; each R, R′, R A , R B , R C , and R D is independently hydrogen or a substituent; any two substituents may be joined or fused together to form a ring; and at least one pair of R B , R C , or R D are joined to form a 5-membered heterocyclic ring. Formulations, OLEDs, and consumer products containing the compound are also provided.
1 . A compound comprising a structure of Formula I,
wherein: M is Pt;
each of moieties B, C, and D is independently a monocyclic or fused multicyclic ring system comprising one or more 5-membered or 6-membered carbocyclic or heterocyclic rings;
each of X 1 , X 2 , X 3 , X 4 , and X 5 is independently C or N;
Y 1 is C or N;
each of Z 1 , Z 2 , Z 3 , Z 4 , and Z 5 is independently C or N;
each of K 2 , and K 3 is independently selected from the group consisting of a direct bond, O, and S;
at least one of K 1 , K 2 , and K 3 is O or S;
if Z 1 is N, then K 1 is a direct bond;
if Z 2 is N, then K 2 is a direct bond;
each is independently a single bond or a double bond;
L 1 and L 2 are each independently selected from the group consisting of a direct bond, BR, BRR′, NR, PR, P(O)R, O, S, Se, C═O, C═S, C═Se, C═NR′, C═CR′R″, S═O, SO 2 , CR, CRR′, SiRR′, GeRR′, alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof;
each of R A , R B , R C , and R D independently represents mono to the maximum allowable substitution, or no substitution;
each R, R′, R A , R B , R C , and R D is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, heteroalkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof;
any two substituents may be joined or fused together to form a ring;
at least two R B , R C , and R D substituents are joined to form ring E, a 5-membered heterocyclic ring comprising atoms selected from the group consisting of C, N, O, S, Se, Si, and B, wherein Ring E is not fused with 6-membered aromatic or heteroaromatic ring,
with the proviso that the compound does not include a structure of Formula II,
wherein:
Ring Z is a 5-membered or 6-membered ring;
X is selected from the group consisting of O, S, Se, NR, CRR′, SiRR′, and GeRR′;
K is selected from the group consisting of a direct bond, O, and S; and
Y is C or N.
2 . The compound of claim 1 , wherein each R, R′, R A , R B , R C , and R D is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, heteroalkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.
3 . The compound of claim 1 , wherein each of moieties B, C, and D is independently selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, and fluorene.
4 . The compound of claim 1 , wherein X 1 is N, and exactly one of Z 1 , Z 2 , and Z 3 is N.
5 . The compound of claim 1 , wherein exactly one of K 1 , K 2 , and K 3 is O or S.
6 . The compound of claim 1 , wherein Ring E is fused to moiety B; or Ring E is fused to moiety C; or Ring E is fused to moiety D.
7 . The compound of claim 1 , wherein L 1 is a direct bond.
8 . The compound of claim 1 , wherein L 1 is selected from the group consisting of O, S, NR, and Se; and/or wherein L 2 is selected from the group consisting of O, S, NR and Se.
9 . The compound of claim 1 , wherein L 2 is a direct bond.
10 . The compound of claim 1 , wherein Ring E comprises atoms selected from the group consisting of C, N, O, and S.
11 . The compound of claim 1 , wherein Ring E is further substituted by one or more R E selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof.
12 . The compound of claim 1 , wherein Ring E is further substituted by one or more R E comprising an aryl moiety or a heteroaryl moiety.
13 . The compound of claim 1 , wherein the compound is selected from the group consisting of compounds having the formula of Pt(L A′ )(Ly):
wherein L A′ is selected from the group consisting of:
wherein L y is selected from the group consisting of:
wherein:
Z 2 is C and Z 3 is N, or Z 2 is N and Z 3 is C;
each of X 1 , X 2 , X 2 ′, X 3 , and X 3 ′ is independently selected from the group consisting of O, S and NR″;
each of R A1 , R A2 , R A3 , R A4 , and R A5 is independently represents mono to the maximum allowable substitution, or no substitution;
each R A1 , R A1′ , R A2 , R A2′ , R A3 , R A4′ , R A4 , R A4′ , R A5 , and R A5′ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, heteroalkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof; and
any two substituents may be joined or fused together to form a ring.
14 . The compound of claim 1 , wherein the compound is selected from the group consisting of compounds having the formula of Pt(L A′ )(Ly);
wherein L A ′ has a structure selected from the group consisting of L A′ 1-(R a5 )(R a6 )(R a7 )(X 2 ) to L A′ 52-(R a5 )(R a6 )(X 2 ), wherein each of R a5 , R a6 , and R a7 is independently selected from the group consisting of R1 to R331, and X 2 is selected from the group consisting of X1 to X70, and wherein L A′ 1-(R1)(R1)(R1)(X1) to L A′ 52-(R331)(R331)(X70) have the structures defined as follows:
L A
Structure of L A
L A′ 1-(R1)(R1)(R1)(X1) to L A′ 1- (R331)(R331)(R331) (X70), have the structure
L A′ 2-(R1)(R1)(R1)(X1) to L A′ 2- (R331)(R331)(R331) (X70), have the structure
L A′ 3-(R1)(R1)(X1) to L A′ 3-(R331)(R331)(X70), have the structure
L A′ 4-(R1)(R1)(X1) to L A′ 4-(R331)(R331)(X70), have the structure
L A′ 5-(R1)(R1)(R1)(X1) to L A′ 5- (R331)(R331)(R331)(X70), have the structure
L A′ 6-(R1)(R1)(R1)(X1) to L A′ 6- (R331)(R331)(R331)(X70), have the structure
L A′ 7-(R1)(R1)(X1) to L A′ 7-(R331)(R331)(X70), have the structure
L A′ 8-(R1)(R1)(X1) to L A′ 8-(R331)(R331)(X70), have the structure
L A′ 9-(R1)(R1)(R1)(X1) to L A′ 9- (R331)(R331)(R331)(X70), have the structure
L A′ 10-(R1)(R1)(R1)(X1) to L A′ 10- (R331)(R331)(R331)(X70), have the structure
L A′ 11-(R1)(R1)(X1) to L A′ 11- (R331)(R331)(X70), have the structure
L A′ 12-(R1)(R1)(X1) to L A′ 12- (R331)(R331)(X70), have the structure
L A′ 13-(R1)(R1)(R1)(X1) to L A′ 13- (R331)(R331)(R331)(X70), have the structure
L A′ 14-(R1)(R1)(R1)(X1) to L A′ 14- (R331)(R331)(R331)(X70), have the structure
L A′ 15-(R1)(R1)(X1) to L A′ 15- (R331)(R331)(X70), have the structure
L A′ 16-(R1)(R1)(X1) to L A′ 16- (R331)(R331)(X70), have the structure
L A′ 17-(R1)(R1)(R1)(X1) to L A′ 17- (R331)(R331)(R331)(X70), have the structure
L A′ 18-(R1)(R1)(R1)(X1) to L A′ 18- (R331)(R331)(R331)(X70), have the structure
L A′ 19-(R1)(R1)(X1) to L A′ 19- (R331)(R331)(X70), have the structure
L A′ 20-(R1)(R1)(X1) to L A′ 20- (R331)(R331)(X70), have the structure
L A′ 21-(R1)(R1)(R1)(X1) to L A′ 21- (R331)(R331)(R331)(X70), have the structure
L A′ 22-(R1)(R1)(R1)(X1) to L A′ 22- (R331)(R331)(R331)(X70), have the structure
L A′ 23-(R1)(R1)(X1) to L A′ 23- (R331)(R331)(X70), have the structure
L A′ 24-(R1)(R1)(X1) to L A′ 24- (R331)(R331)(X70), have the structure
L A′ 25-(R1)(R1)(R1)(X1) to L A′ 25- (R331)(R331)(R331)(X70), have the structure
L A′ 26-(R1)(R1)(R1)(X1) to L A′ 26- (R331)(R331)(R331)(X70), have the structure
L A′ 27-(R1)(R1)(X1) to L A′ 27- (R331)(R331)(X70), have the structure
L A′ 28-(R1)(R1)(X1) to L A′ 28- (R331)(R331)(X70), have the structure
L A′ 29-(R1)(R1)(R1)(X1) to L A′ 29- (R331)(R331)(R331)(X70), have the structure
L A′ 30-(R1)(R1)(R1)(X1) to L A′ 30- (R331)(R331)(R331)(X70), have the structure
L A′ 31-(R1)(R1)(X1) to L A′ 31- (R331)(R331)(X70), have the structure
L A′ 32-(R1)(R1)(X1) to L A′ 32- (R331)(R331)(X70), have the structure
L A′ 33-(R1)(R1)(R1)(X1) to L A′ 33- (R331)(R331)(R331)(X70), have the structure
L A′ 34-(R1)(R1)(R1)(X1) to L A′ 34- (R331)(R331)(R331)(X70), have the structure
L A′ 35-(R1)(R1)(X1) to L A′ 35- (R331)(R331)(X70), have the structure
L A′ 36-(R1)(R1)(X1) to L A′ 36- (R331)(R331)(X70), have the structure
L A′ 37-(R1)(R1)(R1)(X1) to L A′ 37- (R331)(R331)(R331)(X70), have the structure
L A′ 38-(R1)(R1)(R1)(X1) to L A′ 38- (R331)(R331)(R331)(X70), have the structure
L A′ 39-(R1)(R1)(X1) to L A′ 39- (R331)(R331)(X70), have the structure
L A′ 40-(R1)(R1)(X1) to L A′ 40- (R331)(R331)(X70), have the structure
L A′ 41-(R1)(R1)(R1)(X1) to L A′ 41- (R331)(R331)(R331)(X70), have the structure
L A′ 42-(R1)(R1)(R1)(X1) to L A′ 42- (R331)(R331)(R331)(X70), have the structure
L A′ 43-(R1)(R1)(X1) to L A′ 43- (R331)(R331)(X70), have the structure
L A′ 44-(R1)(R1)(X1) to L A′ 44- (R331)(R331)(X70), have the structure
L A′ 45-(R1)(R1)(R1)(X1) to L A′ 45- (R331)(R331)(R331)(X70), have the structure
L A′ 46-(R1)(R1)(R1)(X1) to L A′ 46- (R331)(R331)(R331)(X70), have the structure
L A′ 47-(R1)(R1)(X1) to L A′ 47- (R331)(R331)(X70), have the structure
L A′ 48-(R1)(R1)(X1) to L A′ 48- (R331)(R331)(X70), have the structure
L A′ 49-(R1)(R1)(R1)(X1) to L A′ 49- (R331)(R331)(R331)(X70), have the structure
L A′ 50-(R1)(R1)(R1)(X1) to L A′ 50- (R331)(R331)(R331)(X70), have the structure
L A′ 51-(R1)(R1)(X1) to L A′ 51- (R331)(R331)(X70), have the structure
L A′ 52-(R1)(R1)(X1) to L A′ 52- (R331)(R331)(X70), have the structure
wherein L y has a structure selected from the group consisting of L y 1-(R a1 )(R a2 )(R a3 )(X 3 ) to L y 20-(R a1 )(R a2 )(R a3 )(X 3 )(X 4 ), wherein each of R a1 , R a2 , and R a3 is independently selected from the group consisting of R1 to R331, and each of X 3 and X 4 is independently selected from the group consisting of X1 to X70, and wherein L y 1-(R1)(R1)(R1)(X1) to L y 20-(R331)(R331)(R331)(X70)(X70) have the structures defined as follows:
L y
Structure of L y
L y 1-(R1)(R1)(R1)(X1) to L y 1- (R331)(R331)(R331)(X70), have the structure
L y 2-(R1)(R1)(R1)(X1) to L y 2- (R331)(R331)(R331)(X70), have the structure
L y 3-(R1)(R1)(X1)(X1) to L y 3- (R331)(R331)(X70)(X70), have the structure
L y 4- (R1)(R1)(R1)(X1)(X1) to L y 4-(R331)(R331)(R331) (X70)(X70), have the structure
L y 5-(R1)(R1)(X1)(X1) to L y 5- (R331)(R331)(X70)(X70), have the structure
L y 6- (R1)(R1)(R1)(X1)(X1) to L y 6-(R331)(R331)(R331) (X70)(X70), have the structure
L y 7-(R1)(R1)(X1)(X1) to L y 7- (R331)(R331)(X70)(X70), have the structure
L y 8- (R1)(R1)(R1)(X1)(X1) to L y 8-(R331)(R331)(R331) (X70)(X70), have the structure
L y 9-(R1)(R1)(X1)(X1) to L y 9- (R331)(R331)(X70)(X70), have the structure
L y 10- (R1)(R1)(R1)(X1)(X1) to L y 10- (R331)(R331)(R331) (X70)(X70), have the structure
L y 11-(R1)(R1)(R1)(X1) to L y 11- (R331)(R331)(R331)(X70), have the structure
L y 12-(R1)(R1)(R1)(X1) to L y 12- (R331)(R331)(R331)(X70), have the structure
L y 13-(R1)(R1)(X1)(X1) to L y 13- (R331)(R331)(X70)(X70), have the structure
L y 14- (R1)(R1)(R1)(X1)(X1) to L y 14- (R331)(R331)(R331) (X70)(X70), have the structure
L y 15-(R1)(R1)(X1)(X1) to L y 15- (R331)(R331)(X70)(X70), have the structure
L y 16- (R1)(R1)(R1)(X1)(X1) to L y 16- (R331)(R331)(R331) (X70)(X70), have the structure
L y 17-(R1)(R1)(X1)(X1) to L y 17- (R331)(R331)(X70)(X70), have the structure
L y 18- (R1)(R1)(R1)(X1)(X1) to L y 18- (R331)(R331)(R331) (X70)(X70), have the structure
L y 19-(R1)(R1)(X1)(X1) to L y 19- (R331)(R331)(X70)(X70), have the structure
L y 20- (R1)(R1)(R1)(X1)(X1) to L y 20- (R331)(R331)(R331) (X70)(X70), have the structure
wherein X1 to X70 have the following structures:
and
wherein R1 to R331 have the following structures:
15 . The compound of claim 1 , wherein the compound has a structure of Formula III:
wherein:
each of R* 1 , R* 2 , R* 3 , and R* 4 independently represents mono to the maximum allowable substitution, or no substitution;
each R* 1 , R* 2 , R* 3 , R* 4 or R* 5 is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, heteroalkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof;
any two substituents may be joined or fused together to form a ring; and
one pair of R* 3 , R* 3 , and R* 4 are joined to form ring E, wherein ring E is a 5-membered heterocyclic ring comprising atoms selected from the group consisting of C, N, O, S, Se, Si, and B; and wherein Ring E is not further fused to a 6-membered aromatic or heteroaromatic ring.
16 . The compound of claim 14 , 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 compound comprising a structure of Formula I,
wherein: M is Pt;
each of moieties B, C, and D is independently a monocyclic or fused multicyclic ring system comprising one or more 5-membered or 6-membered carbocyclic or heterocyclic rings;
each of X 1 , X 2 , X 3 , X 4 , and X 5 is independently C or N;
Y 1 is C or N;
each of Z 1 , Z 2 , Z 3 , Z 4 , and Z 5 is independently C or N;
each of K 1 , K 2 , and K 3 is independently selected from the group consisting of a direct bond, O, and S;
at least one of K 1 , K 2 , and K 3 is O or S;
if Z 1 is N, then K 1 is a direct bond;
if Z 2 is N, then K 2 is a direct bond;
each is independently a single bond or a double bond;
L 1 and L 2 are each independently selected from the group consisting of a direct bond, BR, BRR′, NR, PR, P(O)R, O, S, Se, C═O, C═S, C═Se, C═NR′, C═CR′R″, S═O, SO 2 , CR, CRR′, SiRR′, GeRR′, alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof;
each of R A , R B , R C , and R D independently represents mono to the maximum allowable substitution, or no substitution;
each R, R′, R A , R B , R C , and R D is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, heteroalkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof;
any two substituents may be joined or fused together to form a ring;
at least two R B , R C , and R D substituents are joined to form ring E, a 5-membered heterocyclic ring comprising atoms selected from the group consisting of C, N, O, S, Se, Si, and B, wherein Ring E is not fused with 6-membered aromatic or heteroaromatic ring,
with the proviso that the compound does not include a structure of Formula II,
wherein:
Ring Z is a 5-membered or 6-membered ring;
X is selected from the group consisting of O, S, Se, NR, CRR′, SiRR′, and GeRR′;
K is selected from the group consisting of a direct bond, O, and S; and
Y is C or N.
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, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
19 . The OLED of claim 18 , wherein the host is selected from the group consisting of:
and combinations thereof.
20 . 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 compound comprising a structure of Formula I,
wherein: M is Pt;
each of moieties B, C, and D is independently a monocyclic or fused multicyclic ring system comprising one or more 5-membered or 6-membered carbocyclic or heterocyclic rings;
each of X 1 , X 2 , X 3 , X 4 , and X 5 is independently C or N;
Y 1 is C or N;
each of Z 1 , Z 2 , Z 3 , Z 4 , and Z 5 is independently C or N;
each of K 1 , K 2 , and K 3 is independently selected from the group consisting of a direct bond, O, and S;
at least one of K 1 , K 2 , and K 3 is O or S;
if Z 1 is N, then K 1 is a direct bond;
if Z 2 is N, then K 2 is a direct bond;
each is independently a single bond or a double bond;
L 1 and L 2 are each independently selected from the group consisting of a direct bond, BR, BRR′, NR, PR, P(O)R, O, S, Se, C═O, C═S, C═Se, C═NR′, C═CR′R″, S═O, SO 2 , CR, CRR′, SiRR′, GeRR′, alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof;
each of R A , R B , R C , and R D independently represents mono to the maximum allowable substitution, or no substitution;
each R, R′, R A , R B , R C , and R D is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, heteroalkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof;
any two substituents may be joined or fused together to form a ring;
at least two R B , R C , and R D substituents are joined to form ring E, a 5-membered heterocyclic ring comprising atoms selected from the group consisting of C, N, O, S, Se, Si, and B, wherein Ring E is not fused with 6-membered aromatic or heteroaromatic ring,
with the proviso that the compound does not include a structure of Formula II,
wherein:
Ring Z is a 5-membered or 6-membered ring;
X is selected from the group consisting of O, S, Se, NR, CRR′, SiRR′, and GeRR′;
K is selected from the group consisting of a direct bond, O, and S; and
Y is C or N.