Hydrogen bond properties of Se in [ROH-Se(CH)] complexes (R = H, CH, CH): matrix-isolation infrared spectroscopy and theoretical calculations

• Published in: Physical chemistry chemical physics : PCCP 2023-04, Vol.25 (16), p.11286-113
• Main Authors: Pal, Dhritabrata, Agrawal, Sumit Kumar, Chakraborty, Amrita, Chakraborty, Shamik
• Format: Article
• Language: English
• Subjects: Clusters; Electronic structure; Hydrogen bonds; Infrared spectroscopy; Mathematical analysis; Selenium; Spectrum analysis; Vibrational spectra
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d3cp00261f

Se is now considered as a potential centre for hydrogen bond interactions. The hydrogen bond acceptor ability of Se has been investigated in [ROH-Se(CH 3 ) 2 ] complexes (R = H, CH 3 , and C 2 H 5 ) using matrix-isolation infrared spectroscopy and electronic structure calculations. The first impression of the IR spectra of the hydrogen bond complexes of [ROH-Se(CH 3 ) 2 ] in N 2 and Ar matrices is presented here. Moreover, no spectroscopic data are available for the [HOH-Se(CH 3 ) 2 ] complex. Vibrational spectra in the OH stretching region indicate the formation of the [ROH-Se(CH 3 ) 2 ] complex under the matrix-isolation conditions. Comparison of the experimental spectra with the simulated vibrational frequencies at different levels of theory confirms the formation of the 1 : 1 cluster of [ROH-Se(CH 3 ) 2 ] stabilised by O-H Se hydrogen bond interactions. Multiple conformers of the [CH 3 OH-Se(CH 3 ) 2 ] complex having marginally different stabilisation energies have been predicted from electronic structure calculations and signatures of the same have been observed under the cold conditions of matrix isolation. Conformer specific assignment of the 1 : 1 cluster of [C 2 H 5 OH-Se(CH 3 ) 2 ] ( anti and gauche forms) has been carried out in both the matrices. Concentration dependent experiments indicate the formation of higher order clusters and/or mixed clusters along with the formation of a 1 : 1 cluster for CH 3 OH and C 2 H 5 OH. The nature of the selenium centred hydrogen bond has been delineated using AIM, NBO and energy decomposition analysis. A comparison of similar complexes of H 2 O, CH 3 OH, and C 2 H 5 OH with O, S and Se indicates that Se is not far away in hydrogen bond acceptor ability compared to O and S. Se is a potential centre for hydrogen bond interactions.