Organic electroluminescent materials and devices

1. A compound comprising a [n 1 .n 2 .n 3 ]propellane of Formula I:

wherein L 1 comprises a carbon chain having (n 1 -2) carbon atoms, L 2 comprises a carbon chain having (n 2 -2) carbon atoms, and L 3 comprises a carbon chain having (n 3 -2) carbon atoms;

n 1 , n 2 , and n 3 are each independently an integer of 3 or 4;

C 11 -L 1 -C 1n1 forms a first conjugated ring system, C 21 -L 2 -C 2n2 forms a second conjugated ring system, and C 31 -L 3 -C 3n3 forms a third conjugated ring system;

C 31 -L 3 -C 3n3 is selected from the group consisting of:

X is selected from the group consisting of BR, NR, PR, O, S, Se, C═O, S═O, SO 2 , SiRR′, and GeRR′;

R and R′ are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

wherein R and R′ are optionally fused or joined to form a ring;

wherein the first, second and third conjugated ring systems are each optionally further substituted by one or more substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino and combinations thereof;

wherein any two adjacent substituents are optionally fused or joined to form a ring; and

with the proviso that when the first, second and third conjugated ring systems each comprise naphthalene as shown in the following structure:

at least one of the first, second and third conjugated ring systems is substituted by one or more substituents selected from the group consisting of deuterium, alkyl, cycloalkyl, heteroalkyl, arylalkyl, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, wherein any two adjacent substituents are optionally fused or joined to form a 5-member hetero-aromatic ring; and

when the first and second conjugated ring systems each comprise a biphenylene and the third conjugated ring system comprises naphthalene, as shown in the following structure:

the naphthalene ring is substituted by one or more substituents selected from the group consisting of deuterium, alkyl, cycloalkyl, heteroalkyl, arylalkyl, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, wherein any two adjacent substituents are optionally fused or joined to form a 5-member hetero-aromatic ring; and

with the proviso that when the first conjugated ring system comprises biphenylene and the second and third conjugated ring systems each comprise naphthalene or when the second conjugated ring system comprises biphenylene and the first and third conjugated ring systems each comprise naphthalene, as shown in the following structure:

at least one of the naphthalene rings is substituted by one or more substituents selected from the group consisting of deuterium, alkyl, cycloalkyl, heteroalkyl, arylalkyl, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, wherein any two adjacent substituents are optionally fused or joined to form a 5-member hetero-aromatic ring.

2. The compound of claim 1 , wherein the first, and second conjugated ring systems are each an aromatic ring system.

3. The compound of claim 1 , wherein the compound of Formula I is a compound of Formula III:

4. The compound of claim 3 , wherein the first conjugated ring system is naphthalene, and the second conjugated ring system is the same as the third conjugated ring system.

5. 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 comprising a [n 1 .n 2 .n 3 ]propellane of Formula I:

wherein L 1 comprises a carbon chain having (n 1 -2) carbon atoms, L 2 comprises a carbon chain having (n 2 -2) carbon atoms, and L 3 comprises a carbon chain having (n 3 -2) carbon atoms;

n 1 , n 2 , and n 3 are each independently an integer of 3 or 4;

C 11 -L 1 -C n 1 forms a first conjugated ring system, C 21 -L 2 -C 2n2 forms a second conjugated ring system, and C 31 -L 3 -C 3n3 forms a third conjugated ring system;

C 31 -L 3 -C 3n3 is selected from the group consisting of:

X is selected from the group consisting of BR, NR, PR, O, S, Se, C═O, S═O, SO 2 , SiRR′, and GeRR′;

R and R′ are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, and combinations thereof;

wherein R and R′ are optionally fused or joined to form a ring;

wherein the first, second and third conjugated ring systems are each optionally further substituted by one or more substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

wherein any two adjacent substituents are optionally fused or joined to form a ring; and

with the proviso that when the first, second and third conjugated ring systems are each a naphthalene as shown in the following structure:

at least one of the naphthalene rings is substituted by one or more substituents selected from the group consisting of deuterium, alkyl, cycloalkyl, heteroalkyl, arylalkyl, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, and combinations thereof, wherein any two adjacent substituents are optionally fused or joined to form a 5-member hetero-aromatic ring.

6. The OLED of claim 5 , wherein the organic layer is an emissive layer and the compound of Formula I is a host for the emissive layer.

7. The OLED of claim 5 , wherein the organic layer further comprises a phosphorescent emissive dopant;

wherein the emissive dopant is a transition metal complex having at least one ligand, or part of the ligand if the ligand is more than bidentate, selected from the group consisting of:

wherein each X 1 to X 13 are independently selected from the group consisting of carbon and nitrogen;

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;

each R a , R b , R c , and R d may represent from mono substitution to the possible maximum number of substitution, or no substitution;

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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

wherein any two adjacent substituents of R a , R b , R c , and R d are optionally fused or joined to form a ring or form a multidentate ligand.

8. The OLED of claim 5 , wherein the organic layer is a blocking layer and the compound of Formula I is a blocking material in the organic layer, or the organic layer is a transporting layer and the compound of Formula I is a transporting material in the organic layer.

9. The OLED of claim 5 , wherein the OLED is incorporated into a device selected from the group consisting of a consumer product, an electronic component module, and a lighting panel.

10. A formulation comprising a compound of claim 1 .

11. A compound comprising a [n 1 .n 2 .n 3 ]propellane of claim 1

wherein

C 31 -L 3 -C 3n3 is

12. The compound of claim 11 , wherein C 11 -L 1 -C 11 , C 21 -L 2 -C 2n2 are the same or different, and have the structure

13. The compound of claim 12 , wherein C 11 -L 1 -C 1n1 , C 21 -L 2 -C 2n2 , and C 31 -L 3 -C 3n3 are the same.

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

an anode;

a cathode; and an organic layer, disposed between the anode and the cathode, and comprising a compound of claim.

15. The OLED of claim 14 , wherein the organic layer is a blocking layer and the compound of Formula I is a blocking material in the organic layer, or the organic layer is a transporting layer and the compound of Formula I is a transporting material in the organic layer.

16. A compound 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, comprising a compound of claim 16 .