卤素键能的光谱测量
Spectroscopic Measurement of a Halogen Bond Energy.
作者信息
Zhang Xinxing, Liu Gaoxiang, Ciborowski Sandra, Wang Wei, Gong Chu, Yao Yifan, Bowen Kit
机构信息
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center (ReCAST), College of Chemistry, Nankai University, Tianjin, 300071, China.
Departments of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA.
出版信息
Angew Chem Int Ed Engl. 2019 Aug 12;58(33):11400-11403. doi: 10.1002/anie.201906279. Epub 2019 Jul 25.
Halogen bonding (XB) has emerged as an important bonding motif in supramolecules and biological systems. Although regarded as a strong noncovalent interaction, benchmark measurements of the halogen bond energy are scarce. Here, a combined anion photoelectron spectroscopy and density functional theory (DFT) study of XB in solvated Br anions is reported. The XB strength between the positively-charged σ-hole on the Br atom of the bromotrichloromethane (CCl Br) molecule and the Br anion was found to be 0.63 eV (14.5 kcal mol ). In the neutral complexes, Br(CCl Br) , the attraction between the free Br atom and the negatively charged equatorial belt on the Br atom of CCl Br, which is a second type of halogen bonding, was estimated to have interaction strengths of 0.15 eV (3.5 kcal mol ) and 0.12 eV (2.8 kcal mol ).
卤键（XB）已成为超分子和生物系统中一种重要的键合模式。尽管卤键被视为一种强非共价相互作用，但对卤键能的基准测量却很稀少。本文报道了一项结合阴离子光电子能谱和密度泛函理论（DFT）对溶剂化Br阴离子中卤键的研究。发现溴三氯甲烷（CCl₃Br）分子中Br原子上带正电的σ-空穴与Br阴离子之间的卤键强度为0.63电子伏特（14.5千卡·摩尔⁻¹）。在中性配合物Br（CCl₃Br）中，自由Br原子与CCl₃Br分子中Br原子上带负电的赤道带之间的吸引力，这是另一种卤键类型，其相互作用强度估计分别为0.15电子伏特（3.5千卡·摩尔⁻¹）和0.12电子伏特（2.8千卡·摩尔⁻¹）。
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