10.1021/jo902175u.s001
Eric Gagnon
Eric
Gagnon
Shira D. Halperin
Shira D.
Halperin
Valérie Métivaud
Valérie
Métivaud
Kenneth E. Maly
Kenneth E.
Maly
James D. Wuest
James D.
Wuest
Tampering with Molecular Cohesion in Crystals of Hexaphenylbenzenes
American Chemical Society
2010
solubilitie
HOMO
phenyl groups
Molecular Cohesion
HPB
ortho alkyl substituents
interaction
crystal engineering
2010-01-15 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Tampering_with_Molecular_Cohesion_in_Crystals_of_Hexaphenylbenzenes/2799397
Hexaphenylbenzene (HPB) and analogous compounds have properties of broad utility in science and technology, including conformationally well-defined molecular structures, high thermal stability, high HOMO−LUMO gaps, little self-association, inefficient packing, and high solubilities. Previous structural studies of HPB and its analogues have revealed persistent involvement of the central aromatic ring in strong C−H···π interactions. These interactions can be blocked by adding simple ortho alkyl substituents to the peripheral phenyl groups. Comparison of the structures of HPB and a series of ortho-substituted derivatives has shown systematic changes in molecular cohesion and packing, as measured by packing indices, densities, solubilities, temperatures of sublimation, melting points, and ratios of H···H, C···H, and C···C contacts. These results illustrate how crystal engineering can guide the search for improved materials by identifying small but telling molecular alterations that thwart established patterns of association.