| 罗树常,孙小媛,郑鹏飞,刘翔宇,黄仁义.化学通报,2020,83(5):464-471. |
| 同结构GdIIIMII(M=Cu，Ni，Co，Fe，Mn)配合物磁性理论研究 |
| Magnetic Studies of Isomorphous Replacement of MII Ions in {GdIIIMII}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective |
| 投稿时间：2019-11-13 修订日期：2019-12-10 |
| DOI： |
| 中文关键词: GdIIIMII异双核配合物 MII金属离子 磁耦合常数 DFT-BS |
| 英文关键词:GdIIIMII heterobinuclear complexes MII ions Magnetic coupling constant DFT-BS |
| 基金项目:国家自然科学基金项目（21863009）、贵州省科技厅、毕节市科技局、贵州工程应用技术学院联合基金项目（黔科合LH字[2017]7013号，黔科合LH字[2015]7588号）、贵州省教育厅青年科技人才成长项目（黔教合KY字[2017]292号）、毕节市中药材产业化工程研究中心项目（黔教合KY字[2018]009号）、国家级大学生创新创业训练计划项目（201710668010号）和贵州省化学工程与技术重点支持学科项目资助 |
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| 中文摘要: |
| 基于DFT-BS方法，在不同泛函方法和基组下计算[CuIIGdIII{PyCO（OEt）Py C（OH）（OEt）Py}3]2+及3d-Gd异金属双核配合物的磁耦合常数，结果表明，PBE0/TZVP（Gd为SARC-ZDRA-TZVP）水平可用于描述其磁学性质。顺磁中心CuII、GdIII与桥联配位氧原子间存在较强的轨道相互作用，其磁轨道主要由GdIII的4fz3、4fz（x2-y2）轨道、CuII的3dx2-y2轨道和桥联配位原子O的p轨道组成。顺磁中心CuII离子以自旋离域作用为主，GdIII离子以自旋极化作用为主，顺磁中心CuII自旋离域作用对桥联氧原子的影响大于顺磁中心GdIII的自旋极化作用。在同结构3d-Gd配合物中，随着MII离子未成对电子的增加，顺磁中心间ρHS2-ρBS2越大，顺磁中心MII和GdIII之间的反铁磁性贡献越大，其磁耦合常数越小。 |
| 英文摘要: |
| The magnetic properties was studied for a series of {GdIIIMII}(M=Cu, Ni, Co, Fe, Mn) heterobinuclear complexes by the combination of DFT calculations, using the different functional methods and basis sets, with the broken-symmetry approach. The results showed that the calculated values at the level of PBE0/TZVP (Gd is SARC-ZDRA-TZVP) are consistent with the experimental values, and this method can be used to describe its magnetic properties. There is a strong orbital interaction between the paramagnetic centers CuII and GdIII and bridged coordination oxygen atoms. The molecular magnetic orbital of the complex[CuIIGdIII{PyCO(OEt)Py C(OH)(OEt)Py}3]2+ are mainly contributed by 4fz3, 4fz(x2-y2) orbitals of the paramagnetic center GdIII, 3dx2-y2 orbital of CuII ion and p orbitals of the bridging oxygen atoms. Due to the compensation of spin delocalization from CuII ion and spin polarization from GdIII ion, the effect of spin delocalization from CuII ion on bridged oxygen atoms is greater than the spin polarization effect of paramagnetic center GdIII ion. Model calculations were used to examine the influence of the electronic configuration of the MII ions on the magnetic coupling constants. As a result, the increase of unpaired electrons of MII ions, the ρHS2-ρBS2 of the paramagnetic centers GdIII/MIIincreases, the contribution of antiferromagnetic coupling increases, whereas the values of the magnetic coupling constant decreases. |
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