Yuan Mei, Zhao Fei, Zhang Wen, Wang Zhe-Ming, Gao Song
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, PR China.
Inorg Chem. 2007 Dec 24;46(26):11235-42. doi: 10.1021/ic701655w. Epub 2007 Nov 22.
By changing ancillary tetradentate Schiff base ligands (L), two new one-dimensional azide-bridged manganese(III) coordination complexes [MnIII(L)(mu1,3-N3)]n [L = 5-Fsalen (1), 5-OCH3 (2); salen = N,N'-bis(salicylidene)-1,2-diaminoethane] as well as a mononuclear complex [MnIII(salophen)(N3)] (3) [salophen = N,N'-bis(salicylidene)-o-phenylenediamine] have been successfully obtained. All of them have been structurally and magnetically characterized. In the structures of 1-3 each MnIII ion is in a distorted octahedral geometry with an obvious Jahn-Teller effect, where the tetradentate L ligands all bind in the equatorial mode, whereas in the axial direction, the N3- ion acts as an end-to-end bridge in 1 and 2 while a terminal group in 3 with a methanol molecule at the other end. Magnetic characterization shows that the mu1,3-bridging azide ion proves to mainly transmit antiferromagnetic interaction between MnIII ions, but these three complexes exhibit various magnetic behaviors at low temperatures. Noteworthily, complex 2 behaves as a weak ferromagnet with a relatively large coercive field of 2.3 kOe, much larger than the value reported previously.
通过改变辅助四齿席夫碱配体(L),成功获得了两种新型的一维叠氮桥联锰(III)配位络合物[MnIII(L)(μ1,3-N3)]n [L = 5-Fsalen(1),5-OCH3(2);salen = N,N'-双(水杨基亚甲基)-1,2-二氨基乙烷]以及单核络合物[MnIII(salophen)(N3)](3)[salophen = N,N'-双(水杨基亚甲基)-邻苯二胺]。所有这些都已通过结构和磁性表征。在1-3的结构中,每个MnIII离子都处于具有明显 Jahn-Teller 效应的扭曲八面体几何构型中,其中四齿L配体均以赤道模式配位,而在轴向方向上,N3-离子在1和2中充当端对端桥,而在3中作为末端基团,另一端有一个甲醇分子。磁性表征表明,μ1,3-桥联叠氮离子主要证明在MnIII离子之间传递反铁磁相互作用,但这三种络合物在低温下表现出各种磁性行为。值得注意的是,络合物2表现为弱铁磁体,具有2.3 kOe的相对较大矫顽场,远大于先前报道的值。