基于具有混合羧酸盐配体的Mn12氧代羧酸盐簇合物的新型单分子磁体[ Mn12O12（CN-o-C6H4CO2）12（CH3CO2）4（H2O）4]* 8 CH 2Cl 2：合成、晶体和电子结构、磁性
New single-molecule magnet based on Mn12 oxocarboxylate clusters with mixed carboxylate ligands, [Mn12O12(CN-o-C6H4CO2)12(CH3CO2)4(H2O)4]*8CH2Cl2: synthesis, crystal and electronic structure, magnetic properties
摘要：
报道了一个新的高对称性Mn_（12）氧代羧酸簇合物[Mn_（12）O_（12）（CN-o-C_6H_4CO_2）_（12）（CH_3CO_2）_4（H_2O）_4]·8CH_2Cl_2（1）.它是通过标准羧酸酯取代法合成的。1的晶体结构属于四面体空间群I41/a。配合物1含有一个[Mn_（12）O_（12）]核，轴向有8个CN-o-C_6H_4CO_2配体，赤道位置有4个CH_3CO_2和4个CN-o-C_6H_4CO_2配体。四个H2O分子与四个Mn原子以交替的上、下、上、下排列键合，指示1：1：1：1异构体。1中的Mn 12分子是通过互补氢C-H自组装而成。相邻Mn 12簇的轴向邻氰基苯甲酸配体参与形成的N键。晶格溶剂分子（CH 2Cl 2）与Mn 12单元弱相互作用，这导致在从母液中除去晶体后立即发生溶剂损失。电子结构和分子内交换参数进行了计算。Mn的3d带较宽，带的重心从费米能级下移。Mn的3d带和2 p的羧酸桥的氧原子之间的重叠是高于在母体Mn 12-乙酸簇。电子结构的这些变化提供了与Mn 12-乙酸盐相比交换相互作用的显著差异。在干燥（无溶剂）的1。在2-300 K温度范围内的直流磁化率测量支持高自旋基态（S = 10）。
英文摘要：
A new high symmetry Mn12 oxocarboxylate cluster [Mn12O12(CN-o-C6H4CO2)12(CH3CO2)4(H2O)4]*8CH2Cl2 (1) with mixed carboxylate ligands is reported. It was synthesized by the standard carboxylate substitution method. 1 crystallizes in the tetragonal space group I41/a. Complex 1 contains a [Mn12O12] core with eight CN-o-C6H4CO2 ligands in the axial positions, four CH3CO2 and four CN-o-C6H4CO2 those in equatorial positions. Four H2O molecules are bonded to four Mn atoms in an alternating up, down, up, down arrangement indicating 1:1:1:1 isomer. The Mn12 molecules in 1 are self-assembled by complementary hydrogen C-H...N bonds formed with participation of the axial o-cyanobenzoate ligands of the adjacent Mn12 clusters. The lattice solvent molecules (CH2Cl2) are weakly interacted with Mn12 units that results in solvent loss immediately after removal of the crystals from the mother liquor. The electronic structure and the intramolecular exchange parameters have been calculated. Mn 3d bands of 1 are rather broad and center of gravity of the bands shifts down from Fermi level. The overlap between Mn 3d bands and 2p ones of the oxygen atoms from carboxylate bridges is higher than in the parent Mn12-acetate cluster. These changes in electronic structure provide significant difference in the exchange interactions in comparison to Mn12-acetate. The magnetic properties have been studied on a dried (solvent-free) polycrystalline sample of 1. The dc magnetic susceptibility measurements in the 2-300 K temperature range support a high-spin ground state (S = 10).
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