Hassanein K, Amo-Ochoa P, Gómez-García C J, Delgado S, Castillo O, Ocón P, Martínez J I, Perles J, Zamora F
Departamento de Química Inorgánica, Universidad Autónoma de Madrid (UAM) , 28049 Madrid, Spain.
Instituto de Ciencia Molecular (ICMol), Parque Científico, Universidad de Valencia , Catedrático José Beltrán, 2, 46980 Paterna Valencia, Spain.
Inorg Chem. 2015 Nov 16;54(22):10738-47. doi: 10.1021/acs.inorgchem.5b01754. Epub 2015 Oct 26.
The properties recently reported on the Cu(I)-iodide pyrimidine nonporous 1D-coordination polymer [CuI(ANP)]n (ANP = 2-amino-5-nitropyridine) showing reversible physically and chemically driven electrical response have prompted us to carry a comparative study with the series of [CuX(ANP)]n (X = Cl (1), X = Br (2), X = CN (4), and X = SCN (5)) in order to understand the potential influence of the halide and pseudohalide bridging ligands on the physical properties and their electrical response to vapors of these materials. The structural characterization of the series shows a common feature, the presence of -X-Cu(ANP)-X- (X = Cl, Br, I, SCN) double chain structure. Complex [Cu(ANP)(CN)]n (4) presents a helical single chain. Additionally, the chains show supramolecular interlinked interactions via hydrogen bonding giving rise to the formation of extended networks. Their luminescent and electrical properties have been studied. The results obtained have been correlated with structural changes. Furthermore, the experimental and theoretical results have been compared using the density functional theory (DFT). The electrical response of the materials has been evaluated in the presence of vapors of diethyl ether, dimethyl methylphosphonate (DMMP), CH2Cl2, HAcO, MeOH, and EtOH, to build up simple prototype devices for gas detectors. Selectivity toward gases consisting of molecules with H-bonding donor or acceptor groups is clearly observed. This selective molecular recognition is likely due to the 2-amino-5-nitropyridine terminal ligand.
最近报道的碘化亚铜嘧啶无孔一维配位聚合物[CuI(ANP)]n（ANP = 2-氨基-5-硝基吡啶）具有可逆的物理和化学驱动电响应特性，这促使我们对[CuX(ANP)]n系列（X = Cl (1)、X = Br (2)、X = CN (4)和X = SCN (5)）进行比较研究，以了解卤化物和拟卤化物桥连配体对这些材料物理性质及其对蒸汽电响应的潜在影响。该系列的结构表征显示出一个共同特征，即存在-X-Cu(ANP)-X-（X = Cl、Br、I、SCN）双链结构。配合物[Cu(ANP)(CN)]n (4)呈现螺旋单链结构。此外，这些链通过氢键显示出超分子相互连接的相互作用，从而形成扩展网络。研究了它们的发光和电学性质。所获得的结果与结构变化相关。此外，使用密度泛函理论（DFT）对实验和理论结果进行了比较。在二乙醚、甲基膦酸二甲酯（DMMP）、CH2Cl2、HAcO、MeOH和EtOH蒸汽存在下评估了材料的电响应，以构建用于气体探测器的简单原型装置。清楚地观察到对具有氢键供体或受体基团分子组成的气体的选择性。这种选择性分子识别可能归因于2-氨基-5-硝基吡啶末端配体。
