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Spontaneously Organizing Metal Connectors as Supramolecular Structure Directors of Two-and Three-Dimensional Organometallic Assemblies

机译:自发组织金属连接器,作为二维和三维有机金属组装体的超分子结构导向器

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摘要

The supramolecular interplay of Me_3Sn~+ and [M(CN)_2n]~n- ions (n=3 and 4) with either 4,4'-bipyridine (bpy), trans-bis(4-pyridyl)ethene (bpe) or 4-cy-anopyridine (cpy) in the presence of H_2O has been investigated for the first time. Crystal structures of the six novel assemblies: [(Me_3Sn)_4Mo~IV(CN)_8 centre dot 2H_2O centre dot bpe] (8a; isostructural), [(Me_3Sn)_3Fe~III(CN)_6 centre dot 4H_2O centre doty bpy] (9), [(Me_3Sn)_3Co~III(CN)_6 centre dot 3H_2O centre dot 3/2 bpy] (10), [(Me_3Sn)_4Fe~II(CN)_6 centre dot H_2O centre dot 3/2 BPY] (11), and [(Me_3Sn)_4Ru~II(CN)_6 centre dot 2H_2O centre dot 3/2 cpy] (12) are presented. H_2O molecules are usually coordinated to tin atoms and involved in two significant O-H…N hydrogen bonds, wherein the nitrogen atoms belong either to bpy (bpe, cpy) molecules or to M-coordinated cyanide ligands. Extended supramo-lecular assemblies such as -CH-> Sn(Me_3)<-O(H…)->sN(Me_3)-Sn bonds. The supramolecular architecture of 9 involves virtually non-anchored (to cyanide N atoms), Me_3Sn~+ units with a strictly planar SnC_3 skeleton, and two zeolitic H_2O molecules. Pyrazine (pyz) is surprisingly reluctant to afford assemblies similar to 8-12, however, the genuine host-guest systems [(Me_3Sn)_4Mo-(CN)_8 centre dot 0.5pyz] and [(Me_3Sn)_4Mo-(CN)_8 centre dot pym] (pym=pyrimidine) could be isolated and also structurally characterized.
机译:Me_3Sn〜+和[M(CN)_2n]〜n-离子(n = 3和4)与4,4'-联吡啶(bpy),反式双(4-吡啶基)乙烯(bpe)的超分子相互作用首次研究了在H_2O存在下的4-cy-anopyridine(cpy)。六个新颖组件的晶体结构:[(Me_3Sn)_4Mo〜IV(CN)_8中心点2H_2O中心点bpe](8a;同构),[(Me_3Sn)_3Fe〜III(CN)_6中心点4H_2O中心点bpy] (9),[(Me_3Sn)_3Co〜III(CN)_6中心点3H_2O中心点3/2 bpy](10),[(Me_3Sn)_4Fe〜II(CN)_6中心点H_2O中心点3/2 BPY] (11)和[(Me_3Sn)_4Ru〜II(CN)_6中心点2H_2O中心点3/2 cpy](12)被给出。 H_2O分子通常与锡原子配位并参与两个重要的O-H…N氢键,其中氮原子属于bpy(bpe,cpy)分子或M配位的氰化物配体。扩展的超分子组件,例如-CH-> Sn(Me_3)<-O(H…)-> sN(Me_3)- Sn键。 9的超分子结构涉及几乎未锚定的(氰化物N原子),具有严格平面SnC_3骨架的Me_3Sn〜+单元和两个沸石H_2O分子。吡嗪(pyz)令人惊讶地不愿提供类似于8-12的组件,但是,真正的主机-来宾系统[(Me_3Sn)_4Mo-(CN)_8中心点0.5pyz]和[(Me_3Sn)_4Mo-(CN)_8中心点pym](pym =嘧啶)可以被分离并且也可以在结构上表征。

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