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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Synthesis and characterisation of neutral mononuclear cuprous complexes based on dipyrrin derivatives and phosphine
Xiaohui Liu1, Hongmei Nan, Wei Sun
1State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China.
Abstract:
Heteroleptic neutral mononuclear cuprous complexes with dipyrrin derivatives and phosphine mixed-ligands including 1,3,7,9-tetramethyldipyrrin (1), 5-phenyl-1,3,7,9-tetramethyldipyrrin (2), 2,8-dibromo-1,3,7,9-tetramethyldipyrrin (3), 1,9-dichloro-5-phenyldipyrrin (4), 1,9-dibromo-5-phenyldipyrrin (5), 5-pentafluorophenyl-1,3,7,9-tetramethyldipyrrin (6) and 1,5,9-triphenyldipyrrin (7) have been synthesized and fully characterized. The central Cu(i) atoms of these complexes in general formulas of Cu(1-6)(PPh(3))(2) (1a-6a) and Cu(1-6)(DPEphos) (1b-6b) [DPEphos = bis(2-diphenylphosphinophenyl)ether] all exhibit a pseudo-tetrahedral geometry, while complex Cu(7)(PPh(3)) (7a) is tricoordinated in a pyramidal conformation due to the large steric hindrance of ligand 7. The oxidation potentials assigned to oxidations of Cu(i)-Cu(ii) are extraordinarily low in the range of 0.36-1.02 V vs. Ag/AgCl compared with traditional [Cu(phen)(PP)](+) analogues. Their emission maxima range from 495 to 595 nm in dichloromethane at room temperature with quantum yields of 0.05-4.03% and lifetimes on the order of nanoseconds. Unlike the characteristic MLCT emission in cationic Cu(i) complexes, the emissions are assigned to the dipyrrin-centered intraligand charge transition (ILCT) based on the fact that the increased conjugation within the dipyrrinato anion leads to a weaker metal-ligand interaction, thus preventing the mixing of π orbitals of ligand and 3d orbitals of Cu(i) atom. This conclusion is also supported by electrochemical data and theoretical calculations.
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