1,3-二硫代环己烷在银(I)配位聚合物中的桥接模式柔性

L. Brammer, C. S. Rodger, A. Blake, N. R. Brooks, N. Champness, John W. Cunningham, P. Hubberstey, S. Teat, Claire Wilson, M. Schröder
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引用次数: 11

摘要

配位聚合物与Ag∶1,3-二thiane的摩尔比为1∶1,{[Ag2(1,3-二thiane)2][X][Y]}∞(X = Y = no3,1;X = y = pf6, 2;X = y = bf4, 3;X = BF4, Y = Cl, 4;X = Y = NO2, 5和2∶1,{[Ag2(1,3-二thiane)(SO4)(H2O)2]·H2O}∞6,分别合成了一维链和二维片的扩展结构。循环结构基序是[Ag2(μ-1,3-二thiane)2]2+阳离子二聚体,其中两个椅子构象的1,3-二thiane分子充当两个连接单元,以桥接两个Ag(I)中心。在1,2,6中,二聚体通过对桥接阴离子连接成近线性链,形成Ag2X2菱形二聚体。在3中,两个[BF4−]阴离子不是形成Ag2X2(X = F)菱形二聚体,而是形成μ2-F,F ' -桥,支持阳离子之间的弱Ag-S相互作用,形成锯齿状链结构。这种额外的Ag-S接触使1,3-二砜成为一个三连接单元。在4和5中,阳离子二聚体的Ag(I)中心不仅被两个1,3-二硫烷分子桥接,而且还分别被Cl -或NO2 -阴离子桥接,得到[Ag2(μ-1,3-二硫烷)2(μ -Cl)]+(4)和[Ag2(μ-1,3-二硫烷)2(μ -O,O ' -NO2)]+(5)。在4中,Cl−阴离子作为一个μ4桥连接三个[Ag2(μ-1,3-二thiane)2]2+基团,形成一个锯齿状链。在5中,桥接NO2 -阴离子中的一个氧作为μ2桥连接两个[Ag2(μ-1,3-二thiane)2]2+二聚体,形成锯齿状链。虽然1、2、3和5中的碳链是不带电的,但4中的碳链是阳离子的,6中的碳链是阴离子的。4中的电荷平衡由非配位的[BF4−]阴离子维持;5中的配位多面体由“Ag(H2O)2+”维持,其配位多面体由来自单独的1,3-二硫烷分子的硫供体完成,从而作为四个连接单元,并由两个单独的SO42 -阴离子氧组成二维片状结构。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Bridging mode flexibility of 1,3-dithiacyclohexane in silver(I) co-ordination polymers
Co-ordination polymers with Ag∶1,3-dithiane molar ratios of 1∶1, {[Ag2(1,3-dithiane)2][X][Y]}∞ (X = Y = NO3, 1; X = Y = PF6, 2; X = Y = BF4, 3; X = BF4, Y = Cl, 4; X = Y = NO2, 5, and 2∶1, {[Ag2(1,3-dithiane)(SO4)(H2O)2]·H2O}∞6, the extended structures of which are 1-D chains and 2-D sheets, respectively, have been synthesised and structurally characterised. The recurrent structural motif is the [Ag2(μ-1,3-dithiane)2]2+ cationic dimer in which two chair-conformation 1,3-dithiane molecules act as two-connecting units to bridge two Ag(I) centres. In 1, 2, and 6, the dimers are linked into near-linear chains by pairs of bridging anions via formation of an Ag2X2 rhomboid dimer. In 3, instead of forming the Ag2X2 (X = F) rhomboid dimer, two [BF4−] anions form μ2-F,F′-bridges which support weak Ag–S interactions between cations to give a saw-tooth chain structure. This extra Ag–S contact makes the 1,3-dithiane a three-connecting unit. In 4 and 5, the Ag(I) centres of the cationic dimer are bridged not only by two 1,3-dithiane molecules but also by a Cl− or NO2− anion, respectively, to give [Ag2(μ-1,3-dithiane)2(μ2-Cl)]+ (4) and [Ag2(μ-1,3-dithiane)2(μ2-O,O′-NO2)]+ (5). In 4, the Cl− anion acts as a μ4-bridge to link three [Ag2(μ-1,3-dithiane)2]2+ moieties and generate a zig-zag chain. In 5, one oxygen of the bridging NO2− anions acts as a μ2-bridge to link two [Ag2(μ-1,3-dithiane)2]2+ dimers and generate a saw-tooth chain. Although the chains in 1, 2, 3 and 5 are uncharged, that in 4 is cationic and that in 6 is anionic. Charge balance in 4 is maintained by a non-co-ordinated [BF4−] anion; that in 5 is maintained by ‘Ag(H2O)2+’, the co-ordination polyhedron of which is completed by sulfur donors from separate 1,3-dithiane molecules, which thus act as four-connecting units, and by two oxygens of separate SO42− anions to give a two-dimensional sheet structure.
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