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首页> 外文期刊>Chemistry: A European journal >Experimental and computational probes of the nature of halogen bonding: Complexes of bromine-containing molecules with bromide anions
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Experimental and computational probes of the nature of halogen bonding: Complexes of bromine-containing molecules with bromide anions

机译：卤素键性质的实验和计算探针：含溴分子与溴化物阴离子的配合物

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摘要

The nature of halogen bonding is examined via experimental and computational characterizations of a series of associates between electrophilic bromocarbons R-Br (R-Br=CBr_3F, CBr_3NO_2, CBr_3COCBr_3, CBr_3CONH_2, CBr _3CN, etc.) and bromide anions. The [R-Br, Br-] complexes show intense absorption bands in the 200-350 nm range which follow the same Mulliken correlation as those observed for the charge-transfer associates of bromide anions with common organic π-acceptors. For a wide range of the associates, intermolecular R-Br×××Br~- separations decrease and intramolecular C-Br bond lengths increase proportionally to the Br~-→R-Br charge transfer; and the energies of R-Br×××Br~- bonds are correlated with the linear combination of orbital (charge-transfer) and electrostatic interactions. On the whole, spectral, structural and thermodynamic characteristics of the [R-Br, Br~-] complexes indicate that besides electrostatics, the orbital (charge-transfer) interactions play a vital role in the R- Br×××Br~- halogen bonding. This indicates that in addition to controlling the geometries of supramolecular assemblies, halogen bonding leads to electronic coupling between interacting species, and thus affects reactivity of halogenated molecules, as well as conducting and magnetic properties of their solid-state materials. Charge transfer or electrostatics: Experimental and computational characterization of the complexes between bromocarbons and Br~- ions, [R-Br, Br~-] revealed that their structural (inter- and intramolecular bond lengths) and spectral features are directly related to the Br~-→R-Br charge transfer, and their energetics are accounted for by the combination of the charge-transfer and electrostatic interactions. The results indicate that orbital (charge-transfer) interactions play a vital role in the R-Br×××Br~- halogen bonding (see figure).
机译：卤素键的性质是通过亲电溴化碳R-Br（R-Br = CBr_3F，CBr_3NO_2，CBr_3COCBr_3，CBr_3CONH_2，CBr _3CN等）和溴化物阴离子之间的一系列缔合体的实验和计算表征来检查的。 [R-Br，Br-]配合物在200-350 nm范围内显示出很强的吸收带，该吸收带遵循与溴阴离子与常见有机π受体的电荷转移缔合体所观察到的相同的Mulliken相关性。对于大范围的缔合体，分子间R-Br×××Br〜-间距减小，分子内C-Br键长与Br〜-→R-Br电荷转移成比例增加。 R-Br×××Br〜-键的能量与轨道（电荷转移）和静电相互作用的线性组合相关。总体而言，[R-Br，Br〜-]配合物的光谱，结构和热力学特征表明，除静电作用外，轨道（电荷转移）相互作用在R-Br×××Br〜-中也起着至关重要的作用。卤素键。这表明，除了控制超分子组装体的几何形状外，卤素键还导致相互作用的物种之间发生电子偶联，从而影响卤代分子的反应性以及其固态材料的导电和磁性。电荷转移或静电：溴碳与溴离子[R-Br，Br〜-]之间的配合物的实验和计算特征表明，它们的结构（分子间和分子内键长）和光谱特征与溴直接相关〜-→R-Br电荷转移及其能量是通过电荷转移和静电相互作用的组合来解释的。结果表明，轨道（电荷转移）相互作用在R-Br×××Br〜-卤素键中起着至关重要的作用（见图）。

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