Infrared spectroscopy and theoretical structure analyses of protonated fluoroalcohol clusters: the impact of fluorination on the hydrogen bond networks. Issue 20 (17th May 2022)

• Record Type: Journal Article
• Authors: Shinkai, Takahiro; Hsu, Po-Jen; Fujii, Asuka; Kuo, Jer-Lai
• Is Part Of: Physical chemistry chemical physics. Volume 24:Issue 20(2022)
• Page Start: 12631
• Page End: 12644
• Publication Date: 2022-05-17
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d2cp01300b
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Fluorine substitution of alkylalcohols strictly inhibits cyclic hydrogen bond structure formation of their protonated clusters. Abstract : To explore the impact of fluorination on the hydrogen bond networks of protonated alkylalcohols, infrared spectroscopy and theoretical computations of protonated 2, 2, 2-trifluoroethanol clusters, H + (TFE) n, ( n = 4–7), were performed. It has been demonstrated that the development of the hydrogen bond networks from a linear type to cyclic types occurs in this size region for the protonated alkylalcohol clusters. In contrast, infrared spectroscopy of H + (TFE) n in the OH/CH stretch region clearly indicated that the linear type structures are held in the whole size range, irrespective of temperature of the clusters. The extensive stable isomer structure search of H + (TFE) n based on our latest sampling approach supported the strong preference of the linear type hydrogen bond networks. Detailed analyses of the free OH stretching vibrational bands evidenced the intra- and intermolecular OH⋯FC interactions in the clusters. In addition, infrared spectra of protonated clusters of 2, 2-difluoroethanol, 2, 2-difluoropropanol, and 3, 3, 3-trifluoropropanol were measured for n = 4 and 5, and their spectra also indicated the effective inhibition of the cyclic hydrogen bond network formation by the fluorination.