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

The synthesis of 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) was performed together with a cage-like structure containing the triphosphane 1,1,1-tris(diphenylphosphinomethyl)ethane (4). The luminescence of these complexes has been studied and they show a red shift upon 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 on the recorded absorption, emission and NMR spectra were analysed and supported by TD-DFT calculations.