Varying the Dimensionality of Cu(II)-Based Coordination Polymers Through Solvent Influence

This work reports the synthesis and structure of a large porous zeotype network observed within compound (1) using {Cu$_{2}$(piv)$_{4}$} as the linking unit (piv = pivalate). The slow in situ formation of the hmt ligand (hexamethylenetetramine) appears to be key in generating a µ$_{4}$-bridging mode of the hmt-node. Attempts to improve the low yield of compound (1) using different solvent layer diffusion methods resulted in the µ$_{3}$-hmt complexes (2) and (3). Both compounds exhibit a 3D network of two intertwined chiral networks. Strong hydrogen bonding present in (3) leads to the formation of intertwined, DNA-like double-helix structures. The use of bulky solvents in the synthesis of compound (4) leads to the structure crystallizing solvent-free. The packing of (4) is dominated by energy minimization, which is achieved when the 1D-“cylinders” pack into the closest possible arrangement. This work highlights the potential for solvent controlled synthesis of extended copper-hmt systems.