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The elusive ≡C-H⋯O complex in the hydrogen bonded systems of Phenylacetylene: A Matrix Isolation Infrared and Ab Initio Study

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Fatima,  Mariyam
Department of Chemical Sciences, Indian Institute of Science Education and Research, Sector 81, Mohali, Punjab, 140 306 India;
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Citation

Karir, G., Fatima, M., & Viswanathan, K. S. (2016). The elusive ≡C-H⋯O complex in the hydrogen bonded systems of Phenylacetylene: A Matrix Isolation Infrared and Ab Initio Study. Journal of Chemical Sciences, 128(10), 1557-1569. doi:10.1007/s12039-016-1166-1.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002B-B90B-F
Abstract
Hydrogen-bonded complexes of phenylacetylene (PhAc) with methanol (MeOH) and diethylether (DEE) were studied using matrix isolation infrared spectroscopy. This study specifically searched for the ≡C-H⋯O hydrogen bonded complex in these systems, which manifest a n-σ* interaction and which is a local minimum on the PhAc-MeOH potential surface, as in the case of PhAc-H2O heterodimer. This n-σ* local minimum eluded observation in gas phase studies and it was therefore thought interesting to look for this isomer in cryogenic matrices. While MeOH can interact with PhAc as both a proton donor (O-H⋯π complex) or a proton acceptor (n-σ* complex), DEE can only manifest the n-σ* isomer. A comparison of the spectral shifts observed in the features of PhAc-MeOH and PhAc-DEE would therefore independently confirm the existence or not of n-σ* complex in both these systems. In addition to the n-σ* complex observed in both the above systems, the O-H⋯π complex was also discerned in the PhAc-MeOH system. These complexes have stabilization energy in the range of 8-25 kJ /mol. The experimental results were corroborated by computations performed at MP2 and M06-2X, levels of theory, using 6-311++G(d,p) and aug-cc-pVDZ basis sets. Single point calculations at the CCSD level of theory were also performed. Atoms-in-molecules (AIM), NBO and LMOEDA analysis were also performed to understand the nature of the intermolecular interactions in these complexes.