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Updated: Jul 5, 2026

Probe Type II Band Alignment in One-Dimensional Van Der Waals Heterostructures Using First-Principles Calculations
Published on: October 12, 2019
Through-space interactions between parallel-offset arenes at the van der Waals distance: 1,8-diarylbiphenylene
Franco Cozzi1, Rita Annunziata, Maurizio Benaglia
1Dipartimento di Chimica Organica e Industriale, Universita' degli Studi di Milano, Milano, Italy. franco.cozzi@unimi.it
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.
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