含大环[Ni([15]aneN_5]^(2+)氰基桥联四核簇合物的合成、结构和磁性质(英文)

Syntheses, Structures and Magnetic Properties of Cyanide-bridge Tetranuclear Clusters Containing [Ni([15]aneN_(5-) macrocycle)]^(2+)

用1,4,7,10,13-五氮十五烷(cpad)作为端基配体,合成了2个同构化合物[{Ni(cpad)}3M(CN)6]2[M(CN)6](ClO4)3·6H2O(M=Cr3+,1;Fe3+,2),其中[M(CN)6]3-通过氰基桥联配位,4个[Ni(cpad)]2+阳离子形成四核簇[{Ni(cpad)}3M(CN)6]3+,游离的[M(CN)6]3-和ClO4-为平衡阴离子。晶体参数如下:1,三方晶系,P3c1空间群,a=1.51441(18)nm,c=3.0807(6)nm,V=6.1189(15)nm3,Z=2;2,三方晶系,P3c1空间群,a=1.49762(17)nm,c=3.0878(5)nm,V=5.9976(14)nm3,Z=2。变温磁化率显示在四核簇内氰基桥联的金属离子之间存在铁磁相互作用。

By using 1,4,7,10,13-pentaazacyclopentadecane （cpad） as terminal ligand, two isomorphous complexes [{Ni（cpad）}3M（CN）6]2[M（CN）6]（ClO4）3·6H2O （M=Cr^3＋, 1; Fe^3＋, 2） are obtained. Crystal data： 1, trigonal, P↑-3c1, a=1.514 41（18） nm, c=3.080 7（6） nm, V=6.118 9（15） nm^3, Z=2; 2, trigonal, P↑-3c1, a=1.497 62（17） nm, c=3.087 8（5） nm, V=5.997 6（14） nm^3, Z=2. Each compound contains a tetrahedron-shaped tetranuclear cluster [{Ni（cpad）}3M（CN）6]^3＋, where [M（CN）6]^3- coordinates to three [Ni（cpad）]^2＋ moieties through cyanide bridges. The positive charge of the cluster is balanced by both the discrete [M（CN）6]^3- and perchlorate anions. The temperature dependent magnetic susceptibility measurements reveal that dominant ferromagnetic interactions are mediated in both compounds, with very weak inter-molecular antiferromagnetic interactions.