US 11,958,870 B2
Spiro-containing platinum(II) emitters with tunable emission energies and syntheses thereof
Chi Ming Che, Hong Kong (CN); Wai Hung Ang, Hong Kong (CN); Mao Mao, Hong Kong (CN); and Gang Cheng, Hong Kong (CN)
Assigned to The University of Hong Kong, Hong Kong (CN)
Appl. No. 16/969,872
Filed by THE UNIVERSITY OF HONG KONG, Hong Kong (CN)
PCT Filed Jan. 18, 2019, PCT No. PCT/CN2019/072312
§ 371(c)(1), (2) Date Aug. 13, 2020,
PCT Pub. No. WO2019/144845, PCT Pub. Date Aug. 1, 2019.
Claims priority of provisional application 62/621,978, filed on Jan. 25, 2018.
Prior Publication US 2021/0261588 A1, Aug. 26, 2021
Int. Cl. H01L 51/50 (2006.01); C07F 15/00 (2006.01); H10K 85/30 (2023.01)
CPC C07F 15/0086 (2013.01) [H10K 85/346 (2023.02)] 17 Claims
OG exemplary drawing
 
1. An asymmetric metal complex, comprising the structure:

OG Complex Work Unit Chemistry
where M is Pt, Ir, W, Fe, Ru, Ni, Cu, Au or Zn; where Ar1 is a substituted or unsubstituted aromatic or heteroaromatic ring where X is N or other electron pair donor;

OG Complex Work Unit Chemistry
is

OG Complex Work Unit Chemistry
and forms a spiro unit with Ca, where Ca is a bridging atom and can be independently: nitrogen, carbon, boron, phosphorus, silicon, sulfur, or a combination thereof and O b is a bond, O, S, NR17, B R17, PR17, CR17R18, or SiR17R18; where Oa is O, S, NR19, B R19, PR19, CR19R20, or SiR19R20; where N1, N2 and N4 are independently unsubstituted or substituted boron, carbon, nitrogen, oxygen, silicon, germanium, phosphorous, sulphur or selenium and n is 1 to 3; where N3 is carbon, boron, nitrogen, oxygen, silicon, phosphorous, sulphur or selenium; and the ring containing N1, N2, N3 and N4 is a saturated, unsaturated or aromatic ring; where R1 is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R2, R3, R4, R5, R6, R7, and R8 are independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R9, R10, R11, R12, R13, R14, R15, and R16 are independently hydrogen, halogen, hydroxyl, an unsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstituted aryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group and where a pair of adjacent R groups can independently form a 5-8 membered aryl or arylalkyl ring which may be interrupted one or more times with O, S, N, or NR21; and where R17, R18, R19, R20, and R21 are independently alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, haloalkyl, arylalkane or arylalkene.
 
9. A tetradentate ligand, comprising the structure:

OG Complex Work Unit Chemistry
where Ar1 is a substituted or unsubstituted aromatic or heteroaromatic ring where X is N or other electron pair donor;

OG Complex Work Unit Chemistry
is

OG Complex Work Unit Chemistry
and forms a spiro unit with Ca, where Ca is carbon or silicon and O b is a bond, O, S, NR17, B R17, PR17, CR17R18, or SiR17R18, where Oa is O, S, NR19, B R19, PR19, CR19R20, or SiR19R20, where N1, N2 and N4 are independently unsubstituted or substituted boron, carbon, nitrogen, oxygen, silicon, germanium, phosphorous, sulphur or selenium and n is 1 to 3; where N3 is carbon, boron, nitrogen, oxygen, silicon, germanium, phosphorous, sulphur or selenium; and the ring containing N1, N2, N3 and N4 is a saturated, unsaturated or aromatic ring; where R1 is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R2, R3, R4, R5, R6, R7, and R8 are independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane or arylalkene; where R9, R10, R11, R12, R13, R14, R15, and R16 are independently hydrogen, halogen, hydroxyl, an unsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstituted aryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group and where a pair of adjacent R groups can independently form a 5-8 membered aryl or arylalkyl ring which may be interrupted one or more times with O, S, N, or NR21; and where R17, R18, R19, R20, and R21 are independently alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, haloalkyl, arylalkane or arylalkene, and wherein when Ar1 is pyridyl or isoquinyl or R1 is halogen then at least one of R10 and R15 is not t-butyl when R9, R11, R12, R13, R14, and R16 are hydrogen.