State Key Laboratory Base of Novel Functional Materials & Preparation Science, Center of Applied Solid State Chemistry Research Ningbo University, Ningbo, 315211, PR China.
Dalton Trans. 2011 Jan 7;40(1):277-86. doi: 10.1039/b916719f. Epub 2010 Nov 12.
Four new Cu(II) complexes {[Cu(4)(bpy)(4)(OH)(4)(H(2)O)(2)]}(NO(3))(2)(C(7)H(5)O(2))(2)·6H(2)O 1, {[Cu(4)(bpy)(4)(OH)(4)(H(2)O)(2)]}(NO(3))(2)(C(5)H(6)O(4))·8H(2)O 2, {[Cu(4)(bpy)(4)(OH)(4)(H(2)O)(2)]}(C(5)H(6)O(4))(2)·16H(2)O 3 and {[Cu(6)(bpy)(6)(OH)(6)(H(2)O)(2)]}(C(8)H(7)O(2))(6)·12H(2)O 4 were synthesized (bpy = 2,2'-bipyridine, H(2)(C(5)H(6)O(4)) = glutaric acid, H(C(7)H(5)O(2)) = benzoic acid, H(C(8)H(7)O(2)) = phenyl acetic acid). The building units in 1-3 are the tetranuclear Cu(4)(bpy)(4)(H(2)O)(2)(μ(2)-OH)(2)(μ(3)-OH)(2) complex cations, and in 4 the hexanuclear Cu(6)(bpy)(6)(H(2)O)(2)(μ(2)-OH)(2)(μ(3)-OH)(4) complex cations, respectively. The tetra- and hexanuclear cluster cores [Cu(4)(μ(2)-OH)(2)(μ(3)-OH)(2)] and [Cu(6)(μ(2)-OH)(2)(μ(3)-OH)(4)] in the complex cations could be viewed as from step-like di- and trimerization of the well-known hydroxo-bridged dinuclear [Cu(2)(μ(2)-OH)(2)] entities via the out-of-plane Cu-O(H) bonds. The complex cations are supramolecularly assembled into (4,4) topological networks via intercationic ππ stacking interactions. The counteranions and lattice H(2)O molecules are sandwiched between the 2D cationic networks to form hydrogen-bonded networks in 1-3, while the phenyl acetate anions and the lattice H(2)O molecules generate 3D hydrogen-bonded anionic framework to interpenetrate with the (4,4) topological cationic networks with the hexanuclear complex cations in the channels. The ferromagnetic coupling between Cu(II) ions in the [Cu(4)(μ(2)-OH)(2)(μ(3)-OH)(2)] cores of 1-3 is significantly stronger via equatorial-equatorial OH(-) bridges than via equatorial-apical ones. The outer and the central [Cu(2)(OH)(2)] unit within the [Cu(6)(μ(2)-OH)(2)(μ(3)-OH)(4)] cluster cores in 4 exhibit weak ferromagnetic and antiferromagnetic interactions, respectively. Results about i.r. spectra, thermal and elemental analyses are presented.
四种新的 Cu(II) 配合物{[Cu(4)(bpy)(4)(OH)(4)(H(2)O)(2)]}(NO(3))(2)(C(7)H(5)O(2))(2)·6H(2)O 1、{[Cu(4)(bpy)(4)(OH)(4)(H(2)O)(2)]}(NO(3))(2)(C(5)H(6)O(4))·8H(2)O 2、{[Cu(4)(bpy)(4)(OH)(4)(H(2)O)(2)]}(C(5)H(6)O(4))(2)·16H(2)O 3 和{[Cu(6)(bpy)(6)(OH)(6)(H(2)O)(2)]}(C(8)H(7)O(2))(6)·12H(2)O 4 被合成出来（bpy=2,2'-联吡啶，H(2)(C(5)H(6)O(4))=戊二酸，H(C(7)H(5)O(2))=苯甲酸，H(C(8)H(7)O(2))=苯乙酸）。1-3 中的结构单元是四核Cu(4)(bpy)(4)(H(2)O)(2)(μ(2)-OH)(2)(μ(3)-OH)(2)配合物阳离子，而在 4 中是六核Cu(6)(bpy)(6)(H(2)O)(2)(μ(2)-OH)(2)(μ(3)-OH)(4)配合物阳离子。在配合物阳离子中，四核和六核簇核[Cu(4)(μ(2)-OH)(2)(μ(3)-OH)(2)]和[Cu(6)(μ(2)-OH)(2)(μ(3)-OH)(4)]可以被看作是通过平面外的 Cu-O(H)键，从众所周知的羟桥双核[Cu(2)(μ(2)-OH)(2)]实体的阶梯式二聚体和三聚体而来。配合物阳离子通过离子间ππ堆积相互作用超分子组装成（4,4）拓扑网络。抗衡离子和晶格 H(2)O 分子在 1-3 中夹在 2D 阳离子网络之间，形成氢键网络，而苯乙酸阴离子和晶格 H(2)O 分子则生成 3D 氢键阴离子骨架，与通道中的六核配合物阳离子的（4,4）拓扑阳离子网络相互贯穿。1-3 中[Cu(4)(μ(2)-OH)(2)(μ(3)-OH)(2)]核内 Cu(II)离子之间的铁磁耦合通过赤道-赤道 OH(-)桥比通过赤道-轴向桥要强得多。4 中[Cu(6)(μ(2)-OH)(2)(μ(3)-OH)(4)]簇核内的外部和中心[Cu(2)(OH)(2)]单元分别表现出弱铁磁和反铁磁相互作用。提供了红外光谱、热分析和元素分析的结果。
