Zhang Shao-Liang, Zhao Xin-Hua, Wang Xin-Yi
State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Dalton Trans. 2015 Sep 14;44(34):15189-97. doi: 10.1039/c5dt00038f.
With three pentadentate macrocyclic ligands, three new Mn(CN)6 based complexes, [Mn(L(N3O2))(H2O)]2Mn(CN)6·3H2O (1), {[Mn(L(N5))]3[Mn(CN)6]2}n (2) and {[Mn(L(N5Me))]3[Mn(CN)6]2}n·10nH2O (3) (L(N3O2) = 2,13-dimethyl-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene, L(N5) = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene, L(N5Me) = 2,6-bis[1-(2-(N-methylamino)ethylimino)ethyl]-pyridine), have been synthesized and characterized structurally and magnetically. The structure of 1 was found to be a linear Mn2(II)Mn(III) trinuclear cluster with two Mn(II) capping groups and one Mn(III) ion connected via two trans-cyano groups. In contrast, compounds 2 and a3 re cyano-bridged 2D networks. Magnetic investigation revealed antiferromagnetic coupling between the Mn(III) and Mn(II) ions via the bridging cyanide groups. Complex 1 showed paramagnetic behavior down to 2.0 K with no sign of SMM behavior. The magnetic coupling constant of J = -1.63 cm(-1) with the Hamiltonian H = -2J(S(Mn(III))·SMn(II)1 + SMn(III)·S(Mn(II)2)) was obtained from the fitting of the magnetic susceptibility. For 2 and 3, ferrimagnetic ordering was observed with magnetic phase transition temperatures (Tc) being 7.5 K and 7.0 K, respectively. These compounds are rare examples of a small number of Mn(CN)6 based magnetic materials.
利用三种五齿大环配体，合成了三种基于[Mn(CN)₆]³⁻的新型配合物，[Mn(L(N₃O₂))(H₂O)]₂Mn(CN)₆·3H₂O (1)、{[Mn(L(N₅))]₃[Mn(CN)₆]₂}ₙ (2) 和 {[Mn(L(N₅Me))]₃[Mn(CN)₆]₂}ₙ·10nH₂O (3)（L(N₃O₂) = 2,13 - 二甲基 - 6,9 - 二氧杂 - 3,12,18 - 三氮杂双环[12.3.1]十八碳 - 1(18),2,12,14,16 - 五烯，L(N₅) = 2,13 - 二甲基 - 3,6,9,12,18 - 五氮杂双环[12.3.1]十八碳 - 1(18),2,12,14,16 - 五烯，L(N₅Me) = 2,6 - 双[1 - (2 - (N - 甲基氨基)乙基亚氨基)乙基]吡啶），并对其进行了结构和磁性表征。发现配合物1的结构为线性Mn₂(II)Mn(III)三核簇，有两个Mn(II)封端基团和一个通过两个反式氰基连接的Mn(III)离子。相比之下，配合物2和3是氰基桥连的二维网络。磁性研究表明，Mn(III)和Mn(II)离子之间通过桥连氰基发生反铁磁耦合。配合物1在低至2.0 K时表现出顺磁行为，没有单分子磁体行为的迹象。通过对磁化率的拟合，得到磁耦合常数J = -1.63 cm⁻¹，哈密顿量H = -2J(S(Mn(III))·SMn(II)1 + SMn(III)·S(Mn(II)2))。对于配合物2和3，观察到亚铁磁有序，磁相变温度（Tc）分别为7.5 K和7.0 K。这些化合物是少数基于[Mn(CN)₆]³⁻的磁性材料的罕见例子。
