Novel Hydrogen‐bonded Three‐dimensional Supramolecular Architectures Containing 2D Honeycomb Networks or 2D Grids

Abstract

Abstract Two new supramolecular complexes, [Cu(H 2 dhbd)(3‐pyOH)(H 2 O)] 2 ·3‐pyOH·2H 2 O ( 1 ) and [Cu 2 (dhbd)(dpa) 2 ‐ (H 2 O)]·6H 2 O ( 2 ) (H 4 dhbd=2,3‐dihydroxybutanedioic acid, 3‐pyOH=3‐hydroxypyridine, dpa=2,2′‐dipyridylamine), have been synthesized in aqueous solution and characterized by single‐crystal X‐ray diffraction, elemental analyses, UV‐Vis and IR spectra, and TGA analysis. X‐ray structural analysis revealed that, through four pairs of strong O···H – O hydrogen bonds, the cyclic dinuclear units in 1 together with four adjacent neighbors are connected into a 2D honeycomb network encapsulating free 3‐pyOH ligands. Unexpectedly, the water‐dimers are fixed in interlayers of 2D honeycomb network and act as hydrogen‐bond bridging to further extend these 2D networks into 3D hydrogen‐bonded framework. Complex 2 includes interesting 2D grids constructed from chiral dinuclear units through strong O···H – O and O···H – N hydrogen bonding, which are extended through other crystallization water molecules into three dimension with channels. Variable‐temperature magnetic susceptibility measurements for both complexes indicate the presence of weak antiferromagnetic exchange interactions between adjacent copper(II) ions.