Coordination chemistry of flexible benzene-1,3,5-tricarboxamide derived carboxylates; notable structural resilience and vaguely familiar packing motifs.

ABSTRACT

Flexible benzene-1,3,5-tricarboxamides (BTAs), organic species well-known for their tendencies to form functional soft-materials by virtue of their complementary hydrogen bonding, are explored as structurally reinforcing supramolecular building blocks in porous coordination polymers. We report the synthesis and characterisation of two related, carboxylate-terminated BTA derivatives, and the structure and functionality of their polymeric Cd(ii) complexes. The polycarboxylate ligand benzene-1,3,5-tricarboxamide tris(phenylacetic acid) H3L1 was prepared, and the analogous trimethyl benzene-1,3,5-tricarboxamide tris acetate Me3L2 was prepared and its single crystal structure elucidated. On reaction with cadmium nitrate in a DMF/H2O mixture, each BTA compound yielded coordination polymer species with columnar packing motifs comparable to the familiar BTA triple helix seen in purely organic systems. In the case of Me3L2, this transformation was achieved through a convenient in situ ester hydrolysis. Complex 1 is a 2-dimensional layered material containing tubular intralayer pores, in which amide-amide hydrogen bonding is a notable structural feature. In contrast, the structure of 2 contains no amide-amide hydrogen bonding, and instead a columnar arrangement of ligand species is linked by trinuclear Cd(ii) cluster nodes into a densely packed three-dimensional framework. The crystal structures revealed both materials exhibited significant solvent-accessible volume, and this was probed with thermal analysis and CO2 and N2 adsorption experiments; complex 2 showed negligible gas uptake, while compound 1 possesses an unusually high CO2 capacity for a two-dimensional material with intralayer porosity and surprising structural resilience to guest exchange, evacuation and exposure to air.