Heterobimetallic Pt(II)–M(I) (M = Cu, Ag) eight-membered macrocyclic complexes with large-bite P,N-ligand bridges

Reaction of a new large-bite P,N-ligand, 2-(N-diphenylphosphinomethyl-N-benzyl)aminopyridine (1) with (COD)PtCl2 and (COD)Pt(CCPh)2 give cis-(L)2PtCl2(2) and trans-(L)2Pt(CCPh)2(3), respectively. Complex 3 reacted with M(I)(M = Cu, Ag) perchlorate using its pyridyl and alkynyl groups to afford a novel type of mixed-metal macrocyclic complexes PtM2(L)2(CCPh)2(ClO4)2(M = Cu, 4; M = Ag, 5). Complex 4 can be converted to the solvated complexes Pt[Cu(solvent)]2(µ-L)2(CCPh)2(ClO4)2(solvent = H2O, 4; CH3CN, 4) by recrystallization of 4 in the corresponding solvents. The crystal structures of complexes 2, 3, 4 and 4·CH2Cl2 and luminescence properties of 3, 4 and 5 have been determined.