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首页> 外文期刊>Chemistry: A European journal >Halogen Bonds in Novel Polyhalogen Monoanions
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Halogen Bonds in Novel Polyhalogen Monoanions

机译：新型多卤代的卤素键

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摘要

Polyhalogen monoanions [X_(2n+1)]~- (X=Cl and Br; n=1, 2, 3, 4, and 5) have been systematically studied using the block-localized wave function (BLW) method, which offers a valence bond (VB) analysis. For each species, the most stable isomer can be described as a central halide anion X~- non-classically bonded to a number of dihalogen molecules X_2 via “halogen bonds”. VB analyses confirm the dominant role of the charge-transfer interaction between the lone pair on X~- and the s-anti-bonding orbital of X_2 molecule (n→σ~*) in X_3 ~- and higher analogues. Thus, our study demonstrates that these halogen bonds are essentially dative covalent interactions. Importantly, the charge-transfer interaction between [X_(2n-1)]~- and X_2 decreases with the increasing n, in accord with the weakening of the Lewis basicity as characterized by the corresponding HOMO energy. The reduction of the charge transfer interaction underscores the reduction of covalence in halogen bonds in [X_(2n+1)]~-. This tendency highlights the anti-cooperative effect in polyhalogen monoanions. All in all, the halogen bond between X~- and nX_2 molecules exhibits the same trends as in X~- with a single X_2 molecule. In other words, halogen bonding in the larger clusters derives from the same bonding mechanism as the [X3]~- anion. As such, the X~-···X_2 halogen bond at different bond lengths forms a gauge of covalence for the entire [X_(2n+1)]~- family.
机译：使用块局部化波函数（BLW）方法系统地研究了多卤代锰杂体[X_（2N + 1）]〜 - （x = CL和BR; n = 1,2,3,4和5），该方法提供价键（VB）分析。对于每个物种，最稳定的异构体可以描述为中央卤化物阴离子X〜 - 通过“卤素键”非典型地键合至多个二卤素分子X_2。 VB分析证实了X_3〜 - X_3〜 - 和更高的X_2分子（N→σ〜*）的唯一对与X_2分子（N→σ〜*）之间的电荷转移相互作用的主导作用。因此，我们的研究表明，这些卤素键基本上是具有共价相互作用。重要的是，[X_（2N-1）]〜 - - 和X_2之间的电荷传递相互作用随着LEWIS碱度的弱化而随着LEWIS碱度的弱化而降低，如相应的HOMO能量所表征。电荷转移相互作用的降低强调[X_（2N + 1）]〜 - 卤素键的减少这种趋势凸显了多卤代单甘油中的反合作效应。总而言之，X〜 - 和NX_2分子之间的卤素键具有与X〜 - 用单个X_2分子相同的趋势。换句话说，在较大簇中的卤素键合得出与[x3]〜 - 阴离子相同的粘合机制。因此，不同键长的X〜 - ···X_2卤素键形成整个[X_（2N + 1）]〜 - 家族的共价尺寸。

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