Issue 19, 2023

How great is the stabilization of crowded polyphenylbiphenyls by London dispersion?

Abstract

Decaphenylbiphenyl (1) and 2,2′,4,4′,6,6′-hexaphenylbiphenyl (2) are bulky molecules expected to be greatly destabilized by steric crowding. Herein, through a combined experimental and computational approach, we evaluate the molecular energetics of crowded biphenyls. This is complemented by the study of phase equilibria for 1 and 2. Compound 1 shows a rich phase behavior, displaying an unusual interconversion between two polymorphs. Surprisingly, the polymorph with distorted molecules of C1 symmetry is found to have the highest melting point and to be the one that is preferentially formed. The thermodynamic results also indicate that the polymorph displaying the more regular D2 molecular geometry has larger heat capacity and is probably the more stable at lower temperatures. The melting and sublimation data clearly reveal the weakening of cohesive forces in crowded biphenyls due to the lower molecular surface area. The experimental quantification of the intramolecular interactions in 1 and 2 indicated, using homodesmotic reactions, a molecular stabilization of about 30 kJ mol−1. We attribute the origin of this stabilization in both compounds to the existence of two parallel-displaced π⋯π interactions between the ortho-phenyl substituents on each side of the central biphenyl. Computational calculations with dispersion-corrected DFT methods underestimate the stabilization in 1, unless the steric crowding is well balanced in a homodesmotic scheme. This work demonstrates that London dispersion forces are important in crowded aromatic systems, making these molecules considerably more stable than previously thought.

Graphical abstract: How great is the stabilization of crowded polyphenylbiphenyls by London dispersion?

Supplementary files

Article information

Article type
Paper
Submitted
30 Oct 2022
Accepted
26 Apr 2023
First published
04 May 2023

Phys. Chem. Chem. Phys., 2023,25, 13359-13375

How great is the stabilization of crowded polyphenylbiphenyls by London dispersion?

C. F. R. A. C. Lima, J. T. Mague, Y. Du, R. A. Pascal and L. M. N. B. F. Santos, Phys. Chem. Chem. Phys., 2023, 25, 13359 DOI: 10.1039/D2CP05085D

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