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首页> 外文期刊>Crystal growth & design >Organic Selenocyanates as Halide Receptors: From Chelation to One-Dimensional Systems
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Organic Selenocyanates as Halide Receptors: From Chelation to One-Dimensional Systems

机译：有机硒氰酸酯作为卤化物受体：从螯合到一维系统

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Organic selenocyanates were recently identified as strong chalcogen bond donors. They also play an important role in biochemistry. Here, we show that 1,2-bis(selenocyanatomethyl)benzene (1) and 1,2,4,5-tetrakis(selenocyanatomethyl)-benzene (2) crystallize from dimethylformamide (DMF) to afford solvates where two ortho-SeCN moieties act as a chelate toward the carbonyl oxygen atom of DMF through strong Se center dot center dot center dot O chalcogen bonds. This result led us to explore their ability to also chelate halide anions (Cl-, Br-) in solution as well as in the solid state, an important issue in view of applications in crystal engineering or organocatalysis. NMR titration experiments provide an association constant between 1 and Cl- of 148 M-1. We also observed the recurrent formation of cocrystal salts from the association of the ChB donors 1 and 2 with the onium salts Ph4PCl, Ph4PBr, and Bu4NCl. We demonstrate that not only mu(2)-halide but also mu(4)-halide structures can be stabilized though ChB interactions, leading to the formation of complex polymeric anionic networks. Continuous shape measure calculations of these mu(4)-halide structures demonstrate that seesaw symmetry best describes the mu(4)-Br- bromide structures, while the smaller chloride anions tend to favor a close-to-tetrahedral mu(4)-Cl- organization, which is also confirmed by density functional theory calculations. Electrostatic surface potential calculations further demonstrate the efficiency of this chelating ortho-bis(selenocyanatomethyl) motif in 1 and 2, with V-s,V-max values reaching 50 kcal mol(-1), to be compared with the simplest benzyl selenocyanate (36.4 kcal mol(-1)) or the reference halogen bond donor F5C6-I (35.7 kcal mol(-1)) in the same conditions.
机译：最近鉴定有机硒氰酸酯作为强的硫致铬键供体。他们在生物化学中也发挥着重要作用。在这里，我们表明1,2-双（硒丙二烷替亚甲基）苯（1）和1,2,4,5-四（SelenoCyanatometomethyl） - 苯（2）从二甲基甲酰胺（DMF）中结晶，得到溶剂化物，其中两个官能 - 秒部分通过强硒中心点中心点中心点O降硫键作为DMF的羰基氧原子的螯合物。这一结果导致我们探讨了他们在液晶工程或有机成分中的应用中阐明了解决方案中的卤化物阴离子（CL-，BR-）以及实体的重要问题。 NMR滴定实验提供148 m-1的1和Cl-1之间的缔源。我们还观察到COCrystal Salts与Chb供体1和2的结合的复发形成，用鎓盐pH4pcl，pH4pbr和bu4ncl。我们证明不仅穆（2） - 卤化物，而且亩（4）纯结构虽然肌肉相互作用可以稳定，导致复合聚合物阴离子网络的形成。这些MU（4）卤化物结构的连续形状测量计算表明，跷跷板对称性最能描述MU（4）溴化物结构，而较较小的氯化物阴离子倾向于有利于近距离四面体MU（4）-Cl - 组织，也通过密度泛函理论计算确认。静电表面电位计算进一步证明了在1和2中，用VS，V-MAT值达到50kcal摩尔（-1）的螯合rOTHO-BIS（Selenocyanatometomethyl）基序的效率，与最简单的苄基硒氰酸酯（36.4kcal在相同条件下，Mol（-1））或参考卤素键供体F5C6-I（35.7kcal（-1））。

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