Through-space interactions between parallel-offset arenes at the van der Waals distance: 1,8-diarylbiphenylene syntheses, structure and QM computations.
A model for studying polar-pi 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 (DeltaG(not equal) vs. sigma(0)). 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.
Cozzi
Franco
F
Dipartimento di Chimica Organica e Industriale, Universita' degli Studi di Milano, Milano, Italy. franco.cozzi@unimi.it
Annunziata
Rita
R
Benaglia
Maurizio
M
Baldridge
Kim K
KK
Aguirre
Gerardo
G
Estrada
Jesús
J
Sritana-Anant
Yongsak
Y
Siegel
Jay S
JS