title: Through-space interactions between parallel-offset arenes at the van der Waals distance: 1,8-diarylbiphenylene syntheses, structure and QM computations.
abstract: 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.
authors.affiliation: Dipartimento di Chimica Organica e Industriale, Universita' degli Studi di Milano, Milano, Italy. franco.cozzi@unimi.it
authors.forename: Franco
authors.initials: F
authors.lastname: Cozzi
authors.forename: Rita
authors.initials: R
authors.lastname: Annunziata
authors.forename: Maurizio
authors.initials: M
authors.lastname: Benaglia
authors.forename: Kim K
authors.initials: KK
authors.lastname: Baldridge
authors.forename: Gerardo
authors.initials: G
authors.lastname: Aguirre
authors.forename: Jesús
authors.initials: J
authors.lastname: Estrada
authors.forename: Yongsak
authors.initials: Y
authors.lastname: Sritana-Anant
authors.forename: Jay S
authors.initials: JS
authors.lastname: Siegel