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Organic ammonium ion-occluded flexible coordination polymers: Thermal activation, structure transformation and proton transfer

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Abstract

Solvothermal reactions of 1,3,5-benzenetricarboxylic acid (H3btc) with cadmium acetate or zinc acetate yielded two compounds formulated as (Me2NH2)[Cd(btc)]·DMA (1) (btc = 1,3,5-benzenetricarboxylate, DMA = N,N-dimethylacetamide) and (Me2NH2)[Zn(btc)]·DMF (2) (DMF = N,N-dimethylformamide). Both are 3-D frameworks with the rutile topology, which are constructed from six-connected dimeric metal cores and three-connected btc linkers. The solvent molecules and counter cations are located in the 1-D channels of the frameworks. A slight difference between the two compounds is the different connectivity modes of the metal atoms with the carboxylate groups of the ligands. However, this slight difference results in distinct flexibilities of the two frameworks. Variable-temperature powder X-ray diffraction studies revealed that the framework of 1 collapses when heated at 180 °C with loss of the guest species, but compound 2 undergoes two structural transformations below 380 °C. Thermogravimetry-infrared spectroscopy analysis for 2 showed that the two structural transformations are induced by separate losses of solvent molecules and counter cations, and that the dimethylammonium cations are eliminated as neutral dimethylamine molecules. IR spectroscopy demonstrated that the protons are transferred from the counter cations onto the uncoordinated carboxylate oxygen atoms on the channel walls. Sorption and proton conduction studies have also been performed for the compounds.

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Authors and Affiliations

  1. MOE Key Laboratory of Bioinorganic and Synthetic Chemistry; State Key Laboratory of Optoelectronic Materials and Technologies; School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, China

    LinHua Xie, JianBin Lin, XiaoMin Liu, Wei Xue, WeiXiong Zhang, JiePeng Zhang & XiaoMing Chen

  2. Key Laboratory of Polyoxometalates Science of Ministry of Education; College of Chemistry, Northeast Normal University, Changchun, 130024, China

    ShuXia Liu

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Xie, L., Lin, J., Liu, X. et al. Organic ammonium ion-occluded flexible coordination polymers: Thermal activation, structure transformation and proton transfer. Sci. China Chem. 53, 2144–2151 (2010). https://doi.org/10.1007/s11426-010-4107-8

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