Tripodal gold(i) polypyridyl complexes and their Cu+ and Zn2+ heterometallic derivatives. Effects on luminescence

Abstract

Three gold(I) tripodal complexes containing the tris(2-pyridylmethyl)amine (TPA) ligand coordinated to Au–PR₃ moieties (PR₃ = 1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane, PTA (1), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane, DAPTA (2) and triphenylphosphane (3)) were prepared together with a cage-like structure containing triphosphane 1,1,1-tris(diphenylphosphinomethyl)ethane (4). The luminescence of these complexes has been studied and they show a red shift upon the formation of heterometallic complexes by reaction with Zn(NO₃)₂, CuCl and [Cu(CH₃CN)₄]BF₄. The different coordination motifs of the Zn²⁺ and Cu⁺ heterometallic species and the resulting changes in the recorded absorption, emission and NMR spectra were analysed and supported by TD-DFT calculations.