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一系列具有 2D 层、1D 链和 0D 簇结构的新型锰(II)磺酸盐-胂酸盐。

A series of new manganese(II) sulfonate-arsonates with 2D layer, 1D chain, and 0D clusters structures.

机构信息

State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, PR China.

出版信息

Inorg Chem. 2010 Apr 5;49(7):3489-500. doi: 10.1021/ic100103k.

Abstract

Hydrothermal reactions of manganese(II) salts with o-sulfophenylarsonic acid (o-HO(3)S-C(6)H(4)-AsO(3)H(2), H(3)L) afforded Mn(3)(L)(2)(H(2)O)(3).H(2)O (1) with a layered structure. When 1,10-phenanthroline (phen), 2,2'-bipyridine (bipy), and 2,2':6',2''-terpyridine (terpy) were used as auxiliary chelating ligands, a series of mixed-ligand manganese(II) sulfonate-arsonates with lower dimensional structures, namely, Mn(HL)(phen)(2).8.5H(2)O (2), Mn(HL)(phen)(2)(H(2)O).2H(2)O (3), [Mn(HL)(bipy)(2)]Mn(H(2)L)(bipy)(2).3H(2)O (4), [Mn(HL)(phen)][Mn(HL)(phen)(H(2)O)] (5), Mn(2)(HL)(phen)(4)(H(2)O)(2).4H(2)O (6), Mn(2)(HL)(phen)(4)(H(2)O)(2).H(2)O (7), Mn(2)(HL)(2)(bipy)(3)(H(2)O).H(2)O (8), Mn(HL)(terpy) (9), Mn(7)(OH)(2)(L)(4)(phen)(8).10H(2)O.phen (10), and Mn(HL)(bipy)(H(2)O).2H(2)O (11) have been obtained. 2-4 are mononuclear (4 contains two different mononuclear cluster units) whereas 5-9 feature three types of isolated dinuclear cluster units in which the two Mn(2+) ions are bridged by one or two sulfonate-arsonate ligands. 10 exhibits an interesting heptanuclear cluster in which the Mn(2+) centers are bridged by arsonate, sulfonate groups and hydroxyl anions. 11 features a one-dimensional (1D) chain in which two neighboring Mn(2+) centers are bridged by an arsonate group of a sulfonate-arsonate ligand. Magnetic measurements indicate that 1 exhibits an unprecedented spin topology and behaves as a homospin ferrimagnet whereas 2-4 are essentially paramagnetic. 5-9 and 11 are weakly antiferromagnetic.

摘要

水热反应锰(II)盐与邻磺基苯胂酸(o-HO(3)S-C(6)H(4)-AsO(3)H(2), H(3)L)生成具有层状结构的 Mn(3)(L)(2)(H(2)O)(3).H(2)O (1)。当 1,10-菲咯啉(phen)、2,2'-联吡啶(bipy)和 2,2':6',2''-三联吡啶(terpy)用作辅助螯合配体时,得到一系列具有较低维结构的混合配体锰(II)磺酸盐-胂酸盐,即Mn(HL)(phen)(2).8.5H(2)O (2)、Mn(HL)(phen)(2)(H(2)O).2H(2)O (3)、[Mn(HL)(bipy)(2)]Mn(H(2)L)(bipy)(2).3H(2)O (4)、[Mn(HL)(phen)][Mn(HL)(phen)(H(2)O)] (5)、Mn(2)(HL)(phen)(4)(H(2)O)(2).4H(2)O (6)、Mn(2)(HL)(phen)(4)(H(2)O)(2).H(2)O (7)、Mn(2)(HL)(2)(bipy)(3)(H(2)O).H(2)O (8)、Mn(HL)(terpy) (9)、Mn(7)(OH)(2)(L)(4)(phen)(8).10H(2)O.phen (10)和 Mn(HL)(bipy)(H(2)O).2H(2)O (11)。2-4 是单核的(4 包含两个不同的单核簇单元),而 5-9 则具有三种类型的孤立的双核簇单元,其中两个 Mn(2+)离子由一个或两个磺酸盐-胂酸盐配体桥接。10 表现出有趣的七核簇,其中 Mn(2+)中心由胂酸根、磺酸盐基团和氢氧根阴离子桥接。11 具有一维(1D)链,其中两个相邻的 Mn(2+)中心由磺酸盐-胂酸盐配体的一个胂酸根桥接。磁测量表明,1 表现出前所未有的自旋拓扑结构,表现为同自旋亚铁磁体,而 2-4 基本上是顺磁体。5-9 和 11 是弱反铁磁体。

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