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.
The ≡C-H..O hydrogen bonded complex in phenylacetylene-methanol system, which is a n-σ* interaction and a local minimum was observed in a cryogenic inert gas solid. This n-σ* local minima had eluded observation in gas phase studies.
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Acknowledgements
GK and MF gratefully acknowledge the fellowship from DST and MHRD, respectively. The authors are also grateful to IISER Mohali, India for the facilities.
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KARIR, G., FATIMA, M. & VISWANATHAN, K.S. The elusive ≡C-H⋯O complex in the hydrogen bonded systems of Phenylacetylene: A Matrix Isolation Infrared and Ab Initio Study. J Chem Sci 128, 1557–1569 (2016). https://doi.org/10.1007/s12039-016-1166-1
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DOI: https://doi.org/10.1007/s12039-016-1166-1