Structural Variability and Gas Adsorption Properties of Coordination Polymers Constructed with Aromatic Multicarboxylic and Bidentate Ligands

The self‐assembly reactions of transition metal ions and 1,3,5‐benzenetricarboxylic acid (H 3 btc) in the presence of auxiliary aromatic bidentate ligands 1,10‐phenanthroline (1,10‐phen) or 4,4′‐bipyridine‐ N , N ′‐dioxide (4,4′‐bpdo) have isolated four coordination polymers [Co 18 (btc) 10 (H 2 O) 6 (OH) 6 (1,10‐phen) 6 ] · 14H 2 O · 3DMF ( 1 ) and [ M 3 (btc) 2 (H 2 O) 4 (4,4′‐bpdo)] · 2H 2 O · 2DMF [ M = Co ( 2 ), Mn ( 3 ), Ni ( 4 )]. Single‐crystal X‐ray diffraction analysis revealed that the M 3 clusters in the structure of 1 – 4 are connected by hydroxyl group oxygen atoms (or oxygen atoms from 4,4′‐bpdo ligands) and carboxyl groups to generate a three‐dimensional framework. The network of final assemblies can be adjusted by varying the type of auxiliary ligands (1,10‐phen, 4,4′‐bpdo). In addition, the gas adsorption properties of 2 are also investigated.