Interpenetrated Uranyl-Organic Frameworks with bor and pts Topology: Structure, Spectroscopy, and Computation.
Interpenetrated Uranyl-Organic Frameworks with bor and pts Topology: Structure, Spectroscopy, and Computation.
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DOI：
10.1021/acs.inorgchem.7b02274
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发表时间：
2017-11
影响因子：
4.6
通讯作者：
Chao Liu;Fang-Yuan Chen;Hongrui Tian;Jing Ai;Weiting Yang;Qingjiang Pan;Zhong‐Ming Sun
中科院分区：
文献类型：
--
作者：
Chao Liu;Fang-Yuan Chen;Hongrui Tian;Jing Ai;Weiting Yang;Qingjiang Pan;Zhong‐Ming Sun
以硅为中心的两个异构四面体配体，分别以3连接三角形单元[(UO2)(COO)3]和4连接双核单元[(UO2)2(COO)4]为配体，合成了两种新型的三维互穿铀酰有机骨架（NH4）4[(UO2)4(L1)3]·6H2O(1)和[(UO2)2(H2O)2L2]·2H2O (2), L1 =四akis(3-carboxyphenyl)silicon, L2 = tetrakis(4-carboxyphenyl)silicon。结构分析表明，1具有2倍互穿阴离子网络，而2具有3倍互穿4,4连接的中性网络，具有pts拓扑结构。用热重分析、红外光谱、紫外-可见光谱和光致发光光谱对两种化合物进行了表征。用相对论密度泛函理论（DFT）研究了10种模型化合物1和2的结构参数、拉伸振动频率和吸收与实验结果吻合较好；时间相关的DFT计算揭示了低能量吸收带源于配体到铀的电荷转移。
Two novel three-dimensional interpenetrated uranyl-organic frameworks, (NH4)4[(UO2)4(L1)3]·6H2O (1) and [(UO2)2(H2O)2L2]·2H2O (2), where L1 = tetrakis(3-carboxyphenyl)silicon and L2 = tetrakis(4-carboxyphenyl)silicon, were synthesized by a combination of two isomeric tetrahedral silicon-centered ligands with 3-connected triangular [(UO2)(COO)3]- and 4-connected dinuclear [(UO2)2(COO)4] units, respectively. Structural analyses indicate that 1 possesses a 2-fold interpenetrating anion bor network, while 2 exhibits a 3-fold interpenetrated 4,4-connected neutral network with pts topology. Both compounds were characterized by thermogravimetric analysis and IR, UV-vis, and photoluminescence spectroscopy. A relativistic density functional theory (DFT) investigation on 10 model compounds of 1 and 2 shows good agreement of the structural parameters, stretching vibrational frequencies, and absorption with experimental results; the time-dependent DFT calculations unravel that low-energy absorption bands originate from ligand-to-uranium charge transfer.