Versatile Hydrogen-Bonded Assemblies of Twisted Tetra[3,4]thienylene Tetracarboxylic Acid with Selective Solvent Sorption

We demonstrated versatile hydrogen-bonded assemblies of a twisted π system with newly synthesized tetra[3,4]thienylene tetracarboxylic acid ThTCA . Due to its twisted saddle-shaped central π aromatic unit with an anisotropic arrangement of carboxyl units, a variety of dimensional solvate molecular crystals could be obtained, in contrast to typical aromatic carboxylic acid derivatives with low-dimensional assemblies. The versatile molecular assemblies could be converged to ThTCA desol by desolvation with a simple annealing technique. ThTCA desol showed selective solvent sorption behavior, which was governed by the solvent association energy and saturated vapor pressure. Especially, ThTCA desol showed the selective sorption of EtOH, among primary alcohols.