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A series of heteroleptic [Cu(N^N)(P^P)][PF6] complexes is reported in which N^N is a di(methylsulfanyl)-1,10-phenanthroline (2,9-, 3,8- or 4,7-(MeS)2phen) or di(methoxy)-1,10-phenanthroline (2,9-, 3,8- or 4,7-(MeO)2phen) and P^P is bis(2-(diphenylphosphano)phenyl)ether (POP) or 4,5-bis(diphenylphosphano)-9,9-dimethylxanthene (xantphos). The effects of the different substituents are investigated through structural, electrochemical and photophysical studies and by using DFT and TD-DFT calculations. Introducing methylsulfanyl groups in the
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