A model for studying polar-π interactions between arenes spaced at van der Waals distances is developed on the basis of peri-diarylbiphenylenes. A set of 1,8-diarylbiphenylenes is synthesized comprising two Hammett series, one with reference to mesityl ring interactions and the other with reference to pentafluorophenyl ring interactions. X-Ray crystal structures of several derivatives are determined. Barriers to rotation of the probe aryl ring are derived from dynamic NMR data and show a trend for the mesityl reference series (ΔG≠vs. σ°). The model is also used as a test for comparison of modern density functional methods, including B3LYP, M06-2X and BMK functionals; dispersive effects are seen to be an important factor in the proper theoretical treatment of arene interactions.
Through space interactions between parallel offset arenes at the van der Waals distance : 1,8-diarylbiphenylene syntheses, structure and QM computations / F. Cozzi, R. Annunziata, M. Benaglia, K. K. Baldridge, G. Aguirre, J. Estrada, Y. Sritana-Anant, J. S. Siegel. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9076. - 10:19(2008), pp. 2686-2694.
Through space interactions between parallel offset arenes at the van der Waals distance : 1,8-diarylbiphenylene syntheses, structure and QM computations
F. CozziPrimo
;R. AnnunziataSecondo
;M. Benaglia;
2008
Abstract
A model for studying polar-π interactions between arenes spaced at van der Waals distances is developed on the basis of peri-diarylbiphenylenes. A set of 1,8-diarylbiphenylenes is synthesized comprising two Hammett series, one with reference to mesityl ring interactions and the other with reference to pentafluorophenyl ring interactions. X-Ray crystal structures of several derivatives are determined. Barriers to rotation of the probe aryl ring are derived from dynamic NMR data and show a trend for the mesityl reference series (ΔG≠vs. σ°). The model is also used as a test for comparison of modern density functional methods, including B3LYP, M06-2X and BMK functionals; dispersive effects are seen to be an important factor in the proper theoretical treatment of arene interactions.Pubblicazioni consigliate
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