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

Four novel coordination polymers, [Zn(HL1)(2)(phen)(2)]center dot 2CH(3)OH center dot 2H(2)O (1), [ZnCl(HL1)(4,4'-bipy)(0.5)] (n) (2), [Cd(HL1)(L-2)(0.5)(2,2'-bipy)(2)]center dot 3H(2)O (3), [Zn(L-3)(0.5)(N-3)(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 {Zn-6} rings as secondary building units (SBUs). Compound 3 presents a dinuclear {Cd-2} structure with two butterflies "flying side by side" fashion. While compound 4 displays a 1D chain structure based on a dinuclear {Zn-2} SBUs. Moreover, the luminescence properties of 1-4 have been also investigated.