SCHEDULED MAINTENANCE
Visible-emitting Cu(i) complexes with N-functionalized benzotriazole-based ligands†
Abstract
Luminescent mono- and dinuclear cationic heteroleptic Cu(I) complexes [Cu(N∧N′)(P)2]+, [Cu(N∧N′)(P∧P)]+ or [Cu2(N∧N′)2(μ-P∧P)2]2+ containing bidentate N-donor ligands (N∧N′) with benzotriazole, pyridine, pyrimidine or substituted triazine moieties in combination with mono- (P) and bidentate (P∧P) phosphines were synthesized and characterized. Eight single-crystal X-ray diffraction structures were obtained and showed marked distortions from the ideal tetrahedral geometry around Cu(I). Cyclic voltammetry on selected complexes showed reduction processes around −2 V vs. ferrocene/ferrocenium and irreversible oxidation close to 1 V. The long-wavelength absorptions were observed in the range of 350 to 450 nm and attributed to MLCT transitions. Upon excitation with near-UV and violet light, the complexes exhibited emissions from bright yellow (max 538 nm) to red (max 637 nm). Emission maxima, luminescence lifetimes and photoluminescence quantum yields that reach up to 0.92 on powder samples resulted in strong dependence on the choice of the coordinated ligands, the acceptor character of the N∧N′ ligands in particular. DFT calculations confirmed the electrochemical and photophysical outcomes and strongly suggested that the emission has a metal-to-ligand charge transfer (MLCT) nature, with intersystem crossing affording triplet emitting states.
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