同结构GdIIIMII(M=Cu，Ni，Co，Fe，Mn)配合物磁性理论研究

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异金属配合物的磁耦合常数，结果表明，PBE0/TZVP(Gd为SARC-DKH-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，顺磁中心间自旋密度平方差越大，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。

Magnetic Studies of Isomorphous Replacement of MII Ions in {GdIIIMII}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective

The magnetic properties was carried out 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. Search Results show that the magnetic coupling constant between paramagnetic centres was calculated to be 0.20 cm-1 under the PBE0/TZVP, Gd as SARC-DKH-TZVP basis set, which agreed well with the experimental value (0.16 cm-1). Accordingly, it could describe the magnetic properties of {GdIIIMII} (M = Cu, Ni, Co, Fe, Mn) heterobinuclear complexes. 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, spin delocalization from CuII ion more than spin polarization from 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 increase of the square error of the HS and BS spin densities of the paramagnetic centers GdIII/CuII, the contribution of antiferromagnetic coupling is increases, whereas the values of the magnetic coupling constant are decreases.