Manipulation of Molecular and Supramolecular Structure in Cobalt(II) Complexes with Tetrachloroterephthalate through the Influence of Different Solvents

The reactions of cobalt acetates with tetrachloroterephthalic acid (H 2 BDC‐Cl 4 ) in different solvents gave two polymeric and one mononuclear Co II complexes. X‐ray single‐crystal structural determination revealed that the ligand BDC‐Cl 4 displays a reliable bridging tecton to construct diverse supramolecular architectures through coordinative bonds or secondary hydrogen‐bonding interactions. The complexes [Co(BDC‐Cl 4 )(DMF) 2 (EtOH) 2 ] n ( 1 ) and {[Co(BDC‐Cl 4 )(DMF) 2 (MeOH) 2 ] · 2DMF} n ( 2 ) demonstrate a one‐dimensional (1D) coordination motif with infinite Co II ‐tetrachloroterephthalate chains, which are tuned by different binding solvent systems of DMF/ethanol (EtOH) and DMF/methanol (MeOH). [Co(DMF) 2 (H 2 O) 4 ] · (BDC‐Cl 4 ) ( 3 ) represents a two‐dimensional (2D) metallosupramolecular network by hydrogen‐bonded bridging between the aqua ligand of the mononuclear complex with the uncoordinated BDC‐Cl 4 solvates. The spectroscopic, thermal, and fluorescent properties of 1 – 3 were also investigated.