Crystal Structures and Luminescence Behaviour of d10 Metal - Organic Complexes with Multipyridine Ligands

Abstract

Six d10 metal–organic complexes with multipyridine ligands, [Cd(terpy)2](NO3)2·2H2O (1), [Cd(terpy)(NO3)2(H2O)] (2), [Hg(terpy)I2] (3), [Zn(tpt)(NO3)(H2O)2]NO3 (4), [Zn2(tpt)2(4,4′-bipy)(4H2O)](NO3)4·4H2O (5), [Zn(tpt)(OAc)2]·5H2O (6) (terpy = 2,2′:6′,2′-terpyridine, tpt = 2,4,6-tri(2-pyridyl)-1,3,5-triazine, 4,4′-bipy = 4,4′-bipyridine) were synthesized and structurally characterized. The abundant hydrogen-bonding interactions extend complex 2 into ladder-like 1D chains, discrete molecules of 4 into a 2D layer structure, complex 5 into a 2D hydrogen-bonded network through linking the hydrogen-bonded ribbons with hexagonal and four-sided rings, and complex 6 into a 3D hydrogen-bonded network through combining water helical chains. Fluorescence analyses of 1–6 in the solid state are investigated at both room temperature and 10 K. The emission spectra of 1–2 show a large red shift, which is ascribed to ligand-to-ligand charge transfer combined with ligand-to-metal charge transfer, whereas emissions of 4–6 all originate from intraligand π-π* transitions. In organic solvents, 1–6 behave very differently and their emission spectra exhibit various luminescences, with an obvious blue shift indicating strong solvent effects. The X-ray diffraction and thermal gravimetric analyses for complexes 1–6 are also reported.