Computational investigations of intermolecular interactions between electron-accepting bromo- and iodo-pentafluorobenzene and electron-donating furan and thiophene. (21st November 2018)

• Record Type: Journal Article
• Authors: Yang, Fang-Ling; Lu, Ka; Yang, Xing; Yan, Chao-Xian; Wang, Rui; Ye, Weichun; Zhou, Pan-Pan; Yang, Zhaoyong
• Is Part Of: New journal of chemistry. Volume 42:Number 24(2018)
• Page Start: 20101
• Page End: 20112
• Publication Date: 2018-11-21
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c8nj04611e
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : C6 F5 X (X = Br, I) exhibits intriguing σ- and π-hole characters, which enable it to accept electrons from the electron-rich atoms or groups in C4 H4 O and C4 H4 S via various intermolecular interactions. Abstract : Bromo- and iodo-pentafluorobenzene (C6 F5 X, X = Br, I) exhibit intriguing σ- and π-hole characters, which are able to accept electrons, whereas furan (C4 H4 O) and thiophene (C4 H4 S) are able to donate electrons because of their electron-rich atoms and groups ( i.e., the O atom and π-ring in C4 H4 O and the π-ring in C4 H4 S). Theoretical investigations of intermolecular interactions in these systems ( i.e., C4 H4 O and C6 F5 Br, C4 H4 S and C6 F5 Br, C4 H4 O and C6 F5 I, and C4 H4 S and C6 F5 I) have been carried out at the M06-2X/aug-cc-pVDZ and wB97-XD/aug-cc-pVDZ levels with and without the counterpoise method, together with single-point calculations at the CCSD(T)/aug-cc-pVDZ level. For the system of C4 H4 O and C6 F5 X (X = Br, I), five different dimers, namely, I–V andI′–V′, which are connected by σ-hole⋯n, σ-hole⋯π and π-hole⋯π bonds, were found. Moreover, for the system of C4 H4 S and C6 F5 Br, four different dimers, namely, VI–IX, which are connected by σ-hole⋯π and π-hole⋯π bonds, were found. However, five dimers, namely, VI′–X′, were found for the system of C4 H4 S and C6 F5 I, which are connected by σ-hole⋯π, π-hole⋯π and σ-hole⋯n bonds. The driving forces for the formation of these dimers were revealed by EDA analyses. NCI, QTAIM and NBO analyses were employed to prove the existence of intermolecular interactions in these dimers and to elucidate their nature. The results presented here will be insightful for the study of other intermolecular systems that involve σ- and π-holes.