Crystal structures and enhanced luminescence of Zn(II) and Cd(II) complexes containing conjugated organic ligands

Abstract

By self-assembly of delocalized organic ligands (L¹ and L²) with Cd(SCN)₂, ZnI₂ and Zn(NCS)₂, three luminescent complexes ZnI₂(L¹)₂ (I), [Cd(L¹)₂(μ_1,3-SCN)₂]_n (II) and Zn(NCS)₂(L²)₂ (III) were obtained (L¹ = 2-{5,5-dimethyl-3-[2-(pyridine-4-yl)ethenyl]cyclohex-2-enylidene}propanedinitrile and L² = 2-{5,5-dimethyl-3-[2-(pyridine-3-yl)ethenyl]cyclohex-2-enylidene}propanedinitrile). The structures of the complexes were determined by single crystal X-ray diffraction analysis (CIF files CCDC nos. 1406116 (I), 1406115 (II), and 1400360 (III)). In complex I, Zn(II) is coordinated by two functional organic ligands and two I^– ions, to form a I₂N₂ distorted tetrahedral geometry. In 1D coordination polymer II, the Cd(II) centers show six-coordinated geometries, two organic ligands and four SCN^– ions involve in coordination with each Cd(II) center. The thiocyanate groups show μ_1,3-SCN bridging coordination modes and the adjacent Cd(II) ions are bridged by double μ_1,3-SCN ions to form an infinite chain. In complex III, Zn(II) is coordinated by two functional organic ligands and two NCS^– groups, to form a N₄ distorted tetrahedral geometry. Compared with the free ligands, the complexes show superior luminescent property with red-shift and enhancement of fluorescence intensity.