Chains, ladders and sheets of d10 metal–organic polymers generated from the flexible bipyridyl ligands

By use of the three-layer diffusion method, reactions of flexible bipyridyl ligands (4,4′-bpp or 3,3′-bpp) with M(II) salts (M = Zn, Cd) and multi-carboxylate ligands resulted in the formation of four interesting d10 metal–organic coordination polymers: [Zn(μ-4,4′-bpp)Br2]n (1), [Zn(μ-4,4′-bpp)(1,2-bdc)]n · nH2O (2), [Zn(μ-3,3′-bpp)(1,3-bdc)]n · nCH3OH · 2nH2O (3) and [Cd(μ-3,3′-bpp)(C4H2O4)]n · 3nH2O (4) (4,4′-bpp = 2,2′-bis(4-pyridylmethyleneoxy)-1,1′-biphenylene; 3,3′-bpp = 2,2 ′-bis(3-pyridylmethyleneoxy)-1,1′-biphenylene; bdc=benzenedicarboxylate, C4H4O4 = fumaric acid). Complex 1 has a 2D sheet structure consisting of two unusual zigzag Zn(II) chains which are nearly perpendicular to each other. Complex 2 is comprised of two-leg ladders, in which [Zn(4,4′-bpp)] chains serve as the side rails and 1,2-bdc ligands serve as the cross rungs. In complex 3, every two 1,3-bdc ligands connect the neighbouring Zn(II)-3,3′-bpp dimetallic rings in η1 coordination modes into an interesting chain structure. Complex 4 consists of an anionic macrocycle-containing cadmium dicarboxylate sheets that are separated by 3,3′-bpp. These d10 metal complexes exhibit high thermal stabilities and strong luminescence efficiencies.

Graphical abstractFour novel coordination polymers, [Zn(μ-4,4′-bpp)Br2]n (1), [Zn(μ-4,4′-bpp)(1,2-bdc)]n · nH2O (2), [Zn(μ-3,3′-bpp)(1,3-bdc)]n · nCH3OH · 2nH2O (3) and [Cd(μ-3,3′-bpp)(C4H2O4)]n · 3nH2O (4), with interesting structural motifs have been synthesized from flexible bipyridyl, carboxylate ligands and d10 metal ions by the three-layer diffusion method. These d10 metal complexes exhibit high thermal stabilities and strong luminescence efficiencies.Figure optionsDownload full-size imageDownload as PowerPoint slide