Intramolecular halogen bonds in 1,2-aryldiyne molecules: a theoretical study

doi:10.1007/s11224-015-0671-z

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	Intramolecular halogen bonds in 1,2-aryldiyne molecules: a theoretical study
	Zhang, Yuchen 2; Lu, Yunxiang 2; Xu, Zhijian1 ; Ding, Hairong 2; Wu, Weihong 2; Liu, Honglai 2
刊名	STRUCTURAL CHEMISTRY
	2016-06
卷号	27 期号:3 页码:907-917
关键词	Intramoleuclar halogen bonds 1,2-aryldiyne compounds M06-2x CSD
ISSN号	1040-0400
DOI	10.1007/s11224-015-0671-z
文献子类	Article
英文摘要	Intramolecular halogen bonds have been the subject of several current experimental and theoretical studies. In this work, intramolecular halogen bonds in a series of 1,2-aryldiyne molecules were investigated using density functional theory calculations at the M06-2x level of theory. For comparison, some dimeric complexes between halogenated aryldiynes and quinolinyl compounds were also considered. The calculated interatomic distances and interaction angles of intramolecular halogen bonds compare fairly well with those determined experimentally, and the triangle motifs retain almost perfectly planar in all the studied molecules. Many of the well-known properties of conventional halogen bonds are reproduced in intramolecular halogen bonds: the interaction strength tends to increase with the enlargement of the atomic radius of halogens (I > Br > Cl); the attachment of electron-withdrawing moieties to halogens leads to much stronger intramolecular halogen bonds; the X center dot center dot center dot N (quinolinyl) interactions are stronger than the X center dot center dot center dot O (carbonyl) halogen bonds. On the basis of the shorter interatomic distances and the larger values of electron densities at the bond critical points, intramolecular halogen bonds become stronger in strength than corresponding intermolecular halogen bonds. However, these interactions have similar structural, energetic, atoms in molecules (AIM), and noncovalent interaction index (NCI) characteristics to traditional halogen bonds. Therefore, these interactions can be recognized as halogen bonds that are primarily electrostatic in nature. Particularly, the formation of intramolecular halogen bonds gives rise to the essential coplanarity of the molecules, whereas the two subunits in the dimeric complexes deviate from planarity to a large degree. In addition, a small number of crystal structures containing intramolecular halogen bonds were retrieved from the Cambridge Structural Database (CSD), to provide more insights into these interactions in crystals. This work not only will extend the knowledge of noncovalent interactions involving halogens as electrophilic centers but also could be very useful in molecular design and synthetic chemistry.
资助项目	National Natural Science Foundation of China[21473054]
WOS关键词	INTERMOLECULAR HYDROGEN-BONDS ; AB-INITIO CALCULATIONS ; ELECTRON-DONORS ; NONCOVALENT INTERACTIONS ; DENSITY FUNCTIONALS ; ANION RECOGNITION ; COMPLEXES ; CHEMISTRY ; DESIGN ; IODINE
WOS研究方向	Chemistry ; Crystallography
语种	英语
出版者	SPRINGER/PLENUM PUBLISHERS
WOS记录号	WOS:000375436800017
内容类型	期刊论文
源URL	[http://119.78.100.183/handle/2S10ELR8/276033]
专题	药物发现与设计中心
通讯作者	Lu, Yunxiang
作者单位	1.Chinese Acad Sci, Drug Discovery & Design Ctr, Shanghai Inst Mat Med, Shanghai 201203, Peoples R China 2.E China Univ Sci & Technol, Dept Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;
推荐引用方式 GB/T 7714	Zhang, Yuchen,Lu, Yunxiang,Xu, Zhijian,et al. Intramolecular halogen bonds in 1,2-aryldiyne molecules: a theoretical study[J]. STRUCTURAL CHEMISTRY,2016,27(3):907-917.
APA	Zhang, Yuchen,Lu, Yunxiang,Xu, Zhijian,Ding, Hairong,Wu, Weihong,&Liu, Honglai.(2016).Intramolecular halogen bonds in 1,2-aryldiyne molecules: a theoretical study.STRUCTURAL CHEMISTRY,27(3),907-917.
MLA	Zhang, Yuchen,et al."Intramolecular halogen bonds in 1,2-aryldiyne molecules: a theoretical study".STRUCTURAL CHEMISTRY 27.3(2016):907-917.