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利用 N-氧化物功能化主体配体的配位聚合物。

Coordination polymers utilizing N-oxide functionalized host ligands.

机构信息

School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.

出版信息

Inorg Chem. 2012 Oct 15;51(20):10657-74. doi: 10.1021/ic300940k. Epub 2012 Sep 27.

Abstract

Pyridyl functionalized host molecules are oxidized to their N-oxide analogues and form a series of coordination polymers and discrete complexes with transition metal cations. Complex {[Ag(3)(NMP)(6)(L1)(2)]·3(ClO(4))}(∞) where L1 = tris(isonicotinoyl-N-oxide)cyclotriguaiacylene, NMP = N-methylpyrrolidone, is a three-dimensional (3-D) 3,6-connected coordination polymer of pyrite-like (pyr) topology and features ligand unsupported argentophilic interactions, while two-dimensional (2-D) 3,6-connected coordination polymers with the rarely reported kagome dual (kgd) topology are found for M(L1)(2) where M = Zn, Cd, Cu. Ligand L2 = tris(nicotinoyl-N-oxide)cyclotriguaiacylene forms a 2-D coordination polymer with 4(4) (sql) grid topology in complexes {[M(L2)(2)(DMF)(2)]·2ClO(4)·8(DMF)}(∞) M = Cd or Cu, DMF = N,N'-dimethylformamide, and a double-linked chain structure in {[Co(L2)(2)(DMF)(2)]·2NO(3)·4(DMF)·H(2)O}(∞), and both types of structure feature hand-shake self-inclusion motifs either within or between the polymers. 2-D coordination networks with 6(3) (hcb) topologies are found in complexes {[M(L3)(NO(3))(2)]·2(DMF)}(∞) (M = Cd, Zn) and {[Cu(5)(L3)(2)Cl(10)(NMP)(4)]}(∞) where L3 = tris(2-pyridylmethyl)cyclotriguaiacylene, while [Ag(2)(L3)(2)(NMP)(4)]·2(BF(4))·2(NMP) has a discrete dimeric structure which again shows hand-shake host-guest interactions supported by π-π stacking.

摘要

吡啶功能化主体分子被氧化为其 N-氧化物类似物,并与过渡金属阳离子形成一系列配位聚合物和离散配合物。配合物{[Ag(3)(NMP)(6)(L1)(2)]·3(ClO(4))}(∞),其中 L1 = 三(异烟酰基-N-氧化物)环三嗪,NMP = N-甲基吡咯烷酮,是一种具有类似黄铁矿(pyr)拓扑结构的三维(3-D)3,6-连接配位聚合物,具有无配体支持的银亲相互作用,而二维(2-D)3,6-连接配位聚合物则具有罕见报道的 kagome 双重(kgd)拓扑结构,用于M(L1)(2),其中 M = Zn、Cd、Cu。配体 L2 = 三(烟酰基-N-氧化物)环三嗪,在配合物{[M(L2)(2)(DMF)(2)]·2ClO(4)·8(DMF)}(∞),M = Cd 或 Cu,DMF = N,N'-二甲基甲酰胺中形成具有 4(4) (sql)网格拓扑结构的 2-D 配位聚合物,和在{[Co(L2)(2)(DMF)(2)]·2NO(3)·4(DMF)·H(2)O}(∞)中形成双链结构,这两种结构类型都具有聚合物内或聚合物间的握手自包含模式。具有 6(3) (hcb)拓扑结构的 2-D 配位网络存在于配合物{[M(L3)(NO(3))(2)]·2(DMF)}(∞) (M = Cd、Zn)和{[Cu(5)(L3)(2)Cl(10)(NMP)(4)]}(∞)中,其中 L3 = 三(2-吡啶基甲基)环三嗪,而[Ag(2)(L3)(2)(NMP)(4)]·2(BF(4))·2(NMP)具有离散的二聚体结构,再次显示出由π-π堆积支持的握手主体-客体相互作用。

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