| 六聚吡咯大环与铀/超铀酰基离子相互作用:成键、热力学和光谱性质 | |
| Interaction Behavior Between Hexa-dentate Polypyrrolic Macrocycles and Actinyl Species: Bonding, Thermodynamic and Spectroscopic Properties | |
| 摘要: 采用全电子相对论密度泛函理论探索多种六聚吡咯大环锕酰基配合物（nAn；n=1~3；An=U，Np and Pu）的电子结构本质、成键规律和化学反应特性。结构优化发现大环配体空穴大小与锕酰离子尺寸相当时，配合物锕酰基采用性对规则的六角双锥结构，而当空穴尺寸相对大时，配合物则采取扭曲结构以降低体系能量。当配体相同时，随着铀、镎、钚变化，An=O伸缩振动频率逐渐变小，这与优化的键长和键级变化规律相一致。QTAIM（quantum theory of atoms in molecule）拓扑分析显示An-N为弱共价单键特征，具有较大离子性成分。依据不同铀源，得到与大环配体的反应自由能均小于146 kJ·mol-1，与实验合成配合物的反应能计算数值相当。对含铀配合物电子吸收光谱计算显示，低能（近红外和可见光区）的吸收带具有全部或较大的配体→金属电荷转移性质贡献。 | |
| 关键词: 低聚吡咯铀和超铀配合物 QTAIM拓扑分析 热力学反应 电子吸收光谱 相对论密度泛函理论 | |
| 基金项目: 国家自然科学基金（No.21671060，21273063）和内蒙古自治区自然科学基金（No.2017MS0222）资助项目。 | |
| Abstract: A relativistic density functional theory (DFT) was used to systematically examine a series of uranyl and transuranyl complexes of N-donor macrocyclic ligands,[(AnO2)(Ln)]2-(labeled as nAn; n=1~3; An=U, Np and Pu). Further comparison was made with[(UO2)(L0)]2-(A) that was experimentally synthesized. Cavities of L1 and L2 macrocycles are found to match well with actinyl ions, but the one of L3 is a lot larger. Consequently, the L3 complexes have to adopt distorted geometry to energetically stabilize systems. Infrared vibrational spectra presented that the An=O stretching frequencies decrease in going from U, Np to Pu. This agrees with the trend of optimized bond lengths of An=O and bond orders. Topological analyses of quantum theory of atoms in molecule (QTAIM) indicate that the An-N bonds have largely ionic character. Depending on different actinyl source, free energies reacting with various macrocyclic ligands were calculated around 146.4 kJ·mol-1, comparable to the calculated values of A. Time-dependent DFT calculations on four uranyl complexes well reproduced absorption spectra of experimentally reported analogue. The absorption bands in the near-IR and visible region have large contribution from ligand-to-metal charge transfer (LMCT), which is responsible for changes of solution color in the process of macrocyclic ligand sensing uranyl species. | |
| Keywords: polypyrrollic uranyl/transuranyl complexes QTAIM analysis thermodynamic reaction electronic spectroscopy relativistic DFT | |
| 投稿时间：2018-01-07 修订日期：2018-03-20 | |
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| 毕艳婷,姚军,沈中辉,张红星,潘清江.六聚吡咯大环与铀/超铀酰基离子相互作用:成键、热力学和光谱性质[J].无机化学学报,2018,34(6):1071-1078. | |
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| Support information: 相关附件： file180013-Supporting Information.doc | |
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