The structures and properties of halogen bonds involving polyvalent halogen in complexes of FXOn (X = Cl, Br; n=0-3)-CH3CN

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	The structures and properties of halogen bonds involving polyvalent halogen in complexes of FXOn (X = Cl, Br; n=0-3)-CH3CN
	Cheng, Na 1; Bi, Fuzhen 1; Liu, Yongjun 1,2; Zhang, Changqiao 1; Liu, Chengbu 1
	2014
发表期刊	NEW JOURNAL OF CHEMISTRY
ISSN	1144-0546
卷号	38 期号:3 页码:1256-1263
文章类型	Article
摘要	To explore the nature of unconventional halogen bonds, the halogen bonds between a series of halides FXOn (X = Cl, Br; n = 0-3) and CH3CN have been studied at M05-2X/6-311++G(d,p), MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ levels. Our calculations reveal that the electrostatic potentials of these hyper-valent halogen atoms are greatly different to those of monovalent halogen atoms and, accordingly, the strength and interaction modes of these halogen bonds show different characteristics. For complexes of monovalent and heptavalent halides, only one interaction mode was found, but for those of tervalent and pentavalent halides, three kinds of stable configurations with different interaction modes were recognized. Configuration I is a linear structure formed by a single halogen bond, while configurations II and III are cyclic structures formed by the cooperation of a halogen bond and a hydrogen bond. From an energy point of view, monovalent halides form the strongest halogen bonds, and heptavalent halides feature the weakest halogen bonds. For tervalent and pentavalent halides, the interaction energies of the three configurations are similar. In the two cyclic configurations of complexes formed by tervalent and pentavalent halides, due to the competition of the halogen bond with the hydrogen bond, the halogen bonds are weaker than that of configuration I. NBO analysis indicates that the three configurations of complexes display different donor-acceptor orbital interactions. AIM and LMO-EDA analysis reveal that the electrostatic interaction is the dominant driving force for the formation of the complexes, and all the halogen and hydrogen bonds in these complexes are closed-shell interactions.; To explore the nature of unconventional halogen bonds, the halogen bonds between a series of halides FXOn (X = Cl, Br; n = 0-3) and CH3CN have been studied at M05-2X/6-311++G(d,p), MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ levels. Our calculations reveal that the electrostatic potentials of these hyper-valent halogen atoms are greatly different to those of monovalent halogen atoms and, accordingly, the strength and interaction modes of these halogen bonds show different characteristics. For complexes of monovalent and heptavalent halides, only one interaction mode was found, but for those of tervalent and pentavalent halides, three kinds of stable configurations with different interaction modes were recognized. Configuration I is a linear structure formed by a single halogen bond, while configurations II and III are cyclic structures formed by the cooperation of a halogen bond and a hydrogen bond. From an energy point of view, monovalent halides form the strongest halogen bonds, and heptavalent halides feature the weakest halogen bonds. For tervalent and pentavalent halides, the interaction energies of the three configurations are similar. In the two cyclic configurations of complexes formed by tervalent and pentavalent halides, due to the competition of the halogen bond with the hydrogen bond, the halogen bonds are weaker than that of configuration I. NBO analysis indicates that the three configurations of complexes display different donor-acceptor orbital interactions. AIM and LMO-EDA analysis reveal that the electrostatic interaction is the dominant driving force for the formation of the complexes, and all the halogen and hydrogen bonds in these complexes are closed-shell interactions.
WOS标题词	Science & Technology ; Physical Sciences
关键词[WOS]	AB-INITIO ; INTERMOLECULAR INTERACTIONS ; ENERGETIC PROPERTIES ; ELECTRON-DENSITY ; IODINE COMPOUNDS ; CHEMISTRY ; INHIBITORS ; DESIGN ; PREDICTIONS ; MOLECULES
收录类别	SCI
语种	英语
WOS研究方向	Chemistry
WOS类目	Chemistry, Multidisciplinary
WOS记录号	WOS:000331805000050
引用统计	被引频次：25[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://210.75.249.4/handle/363003/4283
专题	中国科学院西北高原生物研究所
作者单位	1.Shandong Univ, Sch Chem & Chem Engn, Minist Educ, Key Lab Colloid & Interface Chem, Jinan 250100, Shandong, Peoples R China 2.Chinese Acad Sci, Northwest Inst Plateau Biol, Xining 810001, Qinghai, Peoples R China
推荐引用方式 GB/T 7714	Cheng, Na,Bi, Fuzhen,Liu, Yongjun,et al. The structures and properties of halogen bonds involving polyvalent halogen in complexes of FXOn (X = Cl, Br; n=0-3)-CH3CN[J]. NEW JOURNAL OF CHEMISTRY,2014,38(3):1256-1263.
APA	Cheng, Na,Bi, Fuzhen,Liu, Yongjun,Zhang, Changqiao,&Liu, Chengbu.(2014).The structures and properties of halogen bonds involving polyvalent halogen in complexes of FXOn (X = Cl, Br; n=0-3)-CH3CN.NEW JOURNAL OF CHEMISTRY,38(3),1256-1263.
MLA	Cheng, Na,et al."The structures and properties of halogen bonds involving polyvalent halogen in complexes of FXOn (X = Cl, Br; n=0-3)-CH3CN".NEW JOURNAL OF CHEMISTRY 38.3(2014):1256-1263.