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首页> 外文期刊>Crystal growth & design >Structure Direction, Solvent Effects, and Anion Influences in Halogen-Bonded Adducts of 2,6-Bis(iodoethynyl)pyridine
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Structure Direction, Solvent Effects, and Anion Influences in Halogen-Bonded Adducts of 2,6-Bis(iodoethynyl)pyridine

机译：2,6-双（碘乙炔基）吡啶的卤素键合加合物中的结构方向，溶剂效应和阴离子影响

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摘要

A new divergent and self-complementary halogen bond donor-acceptor molecule 2,6-bis(iodoethynyl)pyridine L has been prepared and structurally characterized, and used to generate a series of extended halogen-bonded adducts with tetrabutylammonium halide salts. The reaction between L and anions such as either bromide or chloride gives the one-dimensional polymeric species {L center dot TBABr} or {L center dot TBACl}, respectively, which contains helical strands linked by C-I center dot center dot center dot X- halogen bonds which partially encapsulate the associated organic cations. Varying the reaction solvent from ethyl acetate to 5:95 methanol/ethyl acetate gives rise to another polymeric phase on combining L with tetrabutylammonium chloride, the one-dimensional looped chain structure {L-2 center dot TBACl} in which each chloride ion acts as a four-connected square planar node for halogen bonding interactions originating from L. Similar solvent effects are observed in the discrete macrocyclic species {L center dot TBAI}-alpha and {L center dot TBAI}-beta, both consisting of cyclic (L2I2)(2-) species which vary in their extended structures to adopt different packing modes, resembling those observed in the chloride and bromide adducts. Reaction of L with tetrabutylammonium fluoride in the presence of methanol gives a one-dimensional polymeric assembly {L2 center dot TBAF center dot MeOH} containing a unique MeOH center dot center dot center dot F- node in which the strongly hydrogen-bonded anionic species is supported solely by four halogen bonding interactions. Excluding hydrogen bond donors from the reaction mixture affords {L(3)TBAF(2)}, an overall two-dimensional polymeric assembly consisting of a mixture of one- and two-dimensional networks based on iodine-fluoride halogen bonds. In all cases, the strong interactions between the iodoethynyl groups and halide anions overcome the tendency for L to form the self-complementary halogen-bonded network, showing that synthetically accessible heterocyclic iodoethynyl compounds present exciting new directions in the structural chemistry field.
机译：已经制备了新的发散的和自互补的卤素键供体-受体分子2，6-双（碘乙炔基）吡啶L，并对其结构进行了表征，并用于与卤化四丁基铵盐生成一系列扩展的卤素键合加合物。 L与阴离子（例如溴离子或氯离子）之间的反应分别生成一维聚合物物种{L中心点TBABr}或{L中心点TBACl}，它们包含由CI中心点中心点中心点X-连接的螺旋链卤素键部分包封了相关的有机阳离子。将反应溶剂从乙酸乙酯变为5:95甲醇/乙酸乙酯会在L与四丁基氯化铵混合后生成另一个聚合物相，该结构是一维环状链结构{L-2中心点TBACl}，其中每个氯离子均作为一个四连接的正方形平面节点，用于源自L的卤素键相互作用。在离散的大环物质{L中心点TBAI} -alpha和{L中心点TBAI} -beta中都观察到类似的溶剂效应，两者均由环状（L2I2）组成（2-）种类，其扩展结构不同，以采用不同的堆积方式，类似于在氯化物和溴化物加合物中观察到的种类。 L与四丁基氟化铵在甲醇存在下的反应生成一维聚合物组件{L2中心点TBAF中心点MeOH}，其中包含独特的MeOH中心点中心点中心点F-节点，其中强氢键合阴离子物种为仅由四个卤素键相互作用支持。从反应混合物中排除氢键供体，得到{L（3）TBAF（2）}，这是一个整体的二维聚合物组件，该组件由基于碘-氟化物卤素键的一维和二维网络的混合物组成。在所有情况下，碘乙炔基与卤化物阴离子之间的强相互作用克服了L形成自互补卤素键网络的趋势，这表明可合成获得的杂环碘乙炔化合物在结构化学领域提出了令人兴奋的新方向。

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