Infrared spectroscopy and theoretical structure analyses of protonated fluoroalcohol clusters: the impact of fluorination on the hydrogen bond networks
Infrared spectroscopy and theoretical structure analyses of protonated fluoroalcohol clusters: the impact of fluorination on the hydrogen bond networks
复制标题
质子化氟代醇簇的红外光谱和理论结构分析：氟化对氢键网络的影响
DOI：
10.1039/d2cp01300b
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Jer-Lai Kuo
中科院分区：
文献类型：
--
作者：
Takahiro Shinkai;Po-Jen Hsu; Asuka Fujii; Jer-Lai Kuo
为了探索氟化对质子化烷基醇氢键网络的影响，对质子化 2,2,2-三氟乙醇簇 H+(TFE)n (n = 4–7) 进行了红外光谱和理论计算。已经证明，质子化烷基醇簇的氢键网络从线性类型到环状类型的发展发生在这个尺寸区域。相比之下，OH/CH 拉伸区域中 H+(TFE)n 的红外光谱清楚地表明，无论簇的温度如何，线性型结构都保持在整个尺寸范围内。基于我们最新的采样方法对 H+(TFE)n 的广泛稳定异构体结构搜索支持了线性型氢键网络的强烈偏好。对自由 OH 伸缩振动带的详细分析证明了簇中分子内和分子间 OH⋯FC 相互作用。此外，测量了n=4和5的2,2-二氟乙醇、2,2-二氟丙醇和3,3,3-三氟丙醇质子化簇的红外光谱，它们的光谱也表明氟化有效抑制了环状氢键网络的形成。
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.