Departament de Química Inorgànica, Instituto de Ciencia Molecular (ICMOL), Universitat de València, 46980 Paterna, València, Spain.
Inorg Chem. 2011 Sep 19;50(18):8694-6. doi: 10.1021/ic201437u. Epub 2011 Aug 15.
Two new heterobimetallic manganese(II)-copper(II) coordination polymers of formulas [Mn(2)Cu(2)(Me(3)mpba)(2)(H(2)O)(6)]·8H(2)O (1) and [Mn(2)Cu(2)(Me(4)ppba)(2)(H(2)O)(6)]·8H(2)O (2) [Me(3)mpba = 2,4,6-trimethyl-N,N'-1,3-phenylenebis(oxamate) and Me(4)ppba = 2,3,5,6-tetramethyl-N,N'-1,4-phenylenebis(oxamate)] have been synthesized following a molecular-programmed self-assembly method from the corresponding dicopper(II) complexes acting as metalloligands toward Mn(II) ions. 1 and 2 consist of neutral Mn(II)(2)Cu(II)(2) layers with a brick-wall structure made up of oxamato-bridged Mn(II)Cu(II) chains connected through double meta- (1) and para-substituted (2) permethylated phenylene spacers. Overall magnetic (1) and nonmagnetic (2) layer ground states result from the ferro- and antiferromagnetic interchain interactions between the oxamato-bridged Mn(II)Cu(II) ferrimagnetic chains across m- and p-phenylene spacers, respectively. Interestingly, compound 1 exhibits a long-range ferromagnetic ordering with a rather high Curie temperature (T(C)) of 20.0 K.
两种新型异双核锰(II)-铜(II)配位聚合物的合成、结构及磁性
两种新的异双核锰(II)-铜(II)配位聚合物的化学式为[Mn(2)Cu(2)(Me(3)mpba)(2)(H(2)O)(6)]·8H(2)O (1) 和 [Mn(2)Cu(2)(Me(4)ppba)(2)(H(2)O)(6)]·8H(2)O (2) [Me(3)mpba = 2,4,6-三甲基-N,N'-1,3-亚苯基双(氧代乙酸根合)和 Me(4)ppba = 2,3,5,6-四甲基-N,N'-1,4-亚苯基双(氧代乙酸根合)] 通过分子编程自组装方法从相应的二铜(II)配合物作为金属配体对 Mn(II)离子进行合成。1 和 2 由中性 Mn(II)(2)Cu(II)(2)层组成,具有砖墙结构,由 oxamato 桥接的 Mn(II)Cu(II)链组成,通过双 meta- (1) 和 para-取代 (2) 全甲基化的亚苯基间隔物连接。整体磁性 (1) 和非磁性 (2) 层基态是由 oxamato 桥接的 Mn(II)Cu(II)反铁磁链之间的铁磁和反铁磁链间相互作用产生的,分别通过 m-和 p-亚苯基间隔物。有趣的是,化合物 1 表现出长程铁磁有序,具有相当高的居里温度 (T(C)) 为 20.0 K。