cg5b01416_si_001.pdf (4.02 MB)
Supramolecular Assembly of Tris(4-carboxyphenyl)arenes: Relationship between Molecular Structure and Solid-State Catenation Motifs
journal contribution
posted on 2016-02-03, 00:00 authored by Holden W. H. Lai, Ren A. Wiscons, Cassandra
A. Zentner, Matthias Zeller, Jesse L. C. RowsellThe
crystal structures of seven 1,3,5-tris(4-carboxyphenyl)arenes
with functionalized central arene rings are reported. The formation
of (6,3) hcb hexagonal sheets as a result of carboxylic
acid dimer formation was observed in most of the crystal structures,
with the exception of two compounds with functional groups capable
of forming hydrogen bonds, namely, 2,4,6-tris(4-carboxyphenyl)-1,3-diaminobenzene
and 2,4,6-tris(4-carboxyphenyl)-3-methylaniline. These structures
were found to incorporate THF solvent molecules in their hydrogen-bonding
motif, giving rise to distorted pseudohexagonal arrays. Functional
groups on the central ring were found to influence stacking distances,
stacking offsets, inclination angles, degree of catenation, and dimensions
of solvent-occupied channels. To better understand and appreciate
these complicated crystal structures, they were categorized into four
distinct stacking/catenation families: simple stacking, single-layer
offset catenation, double-layer offset catenation, and rotated-layer
catenation. The unique structure of the unfunctionalized parent compound
1,3,5-tris(4-carboxyphenyl)benzene is rationalized in light
of the structural behavior of its derivatives.