Sasnovskaya Valentina D, Kopotkov Vyacheslav A, Talantsev Artem D, Morgunov Roman B, Yagubskii Eduard B, Simonov Sergey V, Zorina Leokadiya V, Mironov Vladimir S
Institute of Problems of Chemical Physics, Russian Academy of Sciences , Semenov's av., 1, Chernogolovka, MD, Russian Federation.
Institute of Solid State Physics, Russian Academy of Sciences , Academician Ossipyan str., 2, Chernogolovka, MD, Russian Federation.
Inorg Chem. 2017 Aug 7;56(15):8926-8943. doi: 10.1021/acs.inorgchem.7b00676. Epub 2017 Jul 7.
Two one-dimensional cyano-bridged coordination polymers, namely, {[Mn(dapsc)][Mn(CN)][K(HO)(MeOH)]}·0.5n(HO) (I) and {[Mn(dapsc)][Mn(CN)][K(HO)(MeOH)]} (II), based on alternating high-spin Mn(dapsc) (dapsc = 2,6-diacetylpyridine bis(semicarbazone)) complexes and low-spin orbitally degenerate hexacyanomanganate(III) complexes were synthesized and characterized structurally and magnetically. Static and dynamic magnetic measurements reveal a single-chain magnet (SCM) behavior of I with an energy barrier of U ≈ 40 K. Magnetic properties of I are analyzed in detail in terms of a microscopic theory. It is shown that compound I refers to a peculiar case of SCM that does not fall into the usual Ising and Heisenberg limits due to unconventional character of the Mn-CN-Mn spin coupling resulting from a nonmagnetic singlet ground state of orbitally degenerate complexes [Mn(CN)]. The prospects of [Mn(CN)] complex as magnetically anisotropic molecular building block for engineering molecular magnets are critically analyzed.
基于交替排列的高自旋Mn(dapsc)（dapsc = 2,6 - 二乙酰基吡啶双（氨基脲））配合物和低自旋轨道简并六氰合锰(III)配合物，合成了两种一维氰基桥连配位聚合物，即{[Mn(dapsc)][Mn(CN)][K(HO)(MeOH)]}·0.5n(HO)（I）和{[Mn(dapsc)][Mn(CN)][K(HO)(MeOH)]}（II），并对其进行了结构和磁性表征。静态和动态磁性测量揭示了I具有单链磁体（SCM）行为，其能垒U≈40 K。根据微观理论详细分析了I的磁性。结果表明，化合物I属于SCM的一种特殊情况，由于轨道简并配合物[Mn(CN)]的非磁性单重态基态导致Mn - CN - Mn自旋耦合具有非常规特性，所以它不属于通常的伊辛和海森堡极限情况。对[Mn(CN)]配合物作为用于构建分子磁体的磁各向异性分子构建单元的前景进行了批判性分析。
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