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Published on: March 2, 2016
Triphenylene chromophore enhances emission in Au/Cu heterometallic complexes
Jalal Ahmad1, Anyie P Atencio1, Jas S Ward2
1Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona and Institut de Nanociència i Nanotecnologia (IN2UB), Martí i Franquès 1-11, E-08028 Barcelona, Spain. laurarodriguezr@ub.edu.
Abstract:
Heterometallic Au(I)-Cu(I) assemblies are attractive luminescent platforms due to synergistic metallophilic interactions and enhanced spin-orbit coupling. We report a new family of Au(I)-Cu(I) complexes incorporating a rigid 2-ethynyltriphenylene chromophore and a pyridyldiphenylphosphine auxiliary ligand. Stoichiometric reactions between a mononuclear alkynyl gold(I) precursor and Cu(I) salts bearing different counterions (PF6-, OTf-, BF4-) afford Au2Cu2 assemblies whose structures and packing are strongly counterion-dependent. Single-crystal X-ray diffraction reveals Au-Cu interactions supported by Cu-N(pyridyl) and Cu⋯π(alkynyl) contacts. The photophysical studies show counterion-modulated dual fluorescence/phosphorescence emission in solution, with phosphorescence enhanced under inert conditions. Upon immobilization in polymer matrices, all heterometallic complexes display efficient room-temperature phosphorescence with quantum yields of up to 40% and millisecond lifetimes. These results highlight the role of counterions and matrix rigidification in controlling excited-state deactivation in heterometallic coinage-metal systems.
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