Structure Modulation in Four New Coordination Polymers by In Situ Ligands Synthesis of Anthracene Derivatives and Various Auxiliary N-donor Ligands

Abstract

Four novel coordination polymers, [Zn(HL1)2(phen)2]·2CH3OH·2H2O (1), [ZnCl(HL1)(4,4′-bipy)0.5] n (2), [Cd(HL1)(L2)0.5(2,2′-bipy)2]·3H2O (3), [Zn(L3)0.5(N3)1.5(phen)] n (4) (H2L1 = 9-(1H-tetrazole-5-yl)-10-carboxyl anthracene, H2L2 = 9,10-di-(1H-tetrazole-5-yl) anthracene, HL3 = 9-(1H-tetrazole-5-yl)-10-cyan anthracene, 1,10-phen = 1,10-phenanthroline, 4,4′-bipy = 4,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine), have been constructed by in situ ligands synthesis system. The formation of tetrazole-based ligands H2L1, H2L2 and H2L3 involves the in situ Sharpless [2 + 3] cycloaddition reaction between 9,10-dicyanoanthracene (DCA) and NaN3 in the presence of Zn2+/Cd2+ ions as Lewis-acid catalysts under hydro/solvothermal conditions. At the same time, there is also another in situ carboxyl ligand synthesis reaction by hydrolysis from nitrile in compounds 1 and 2. The four compounds have been characterized by elemental analysis, IR and single-crystal X-ray diffraction analysis. Compound 1 exhibits a butterfly-shaped mononuclear structure. Compound 2 represents a 2D framework constructed by six-membered {Zn6} rings as secondary building units (SBUs). Compound 3 presents a dinuclear {Cd2} structure with two butterflies “flying side by side” fashion. While compound 4 displays a 1D chain structure based on a dinuclear {Zn2} SBUs. Moreover, the luminescence properties of 1–4 have been also investigated.