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Chimera diimine ligands in emissive [Cu(PP)(NN)][PF6] Complexes
The syntheses and characterizations of the chelating ligand 6-chloro-60-methyl-2,20-bipyridine (6-Cl-60-Mebpy) and of the copper(I) compounds [Cu(POP)(6-Cl-60-Mebpy)][PF6] and [Cu(xantphos) (6-Cl-60-Mebpy)][PF6] (POP = bis(2-(diphenylphosphanyl)phenyl)ether and xantphos = 4,5-bis (diphenylphosphanyl)-9,9-dimethyl-9H-xanthene) are described. The single crystal structures of both complexes were determined; the copper(I) ion is in a distorted tetrahedral environment and in [Cu(xantphos)(6-Cl-60-Mebpy)][PF6], the disorder of the 6-Cl-60-Mebpy ligand indicates there is no preference of the ‘bowl’-like cavity of the xanthene unit to host either the methyl or chloro-substituent, consistent with comparable steric effects of the two groups. The electrochemical and photophysical properties of [Cu(POP)(6-Cl-60-Mebpy)][PF6] and [Cu(xantphos)(6-Cl-60-Mebpy)][PF6] were investigated and are compared with those of the related compounds containing 6,60-dichloro-2,20-bipyridine or 6,60-dimethyl-2,20-bipyridine ligands. Trends in properties of the [Cu(PP)(NN)]+ complexes were consistent with 6-Cl-60-Mebpy behaving as a combination of the two parent ligands.
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Reference：
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate