Synthesis, Structural Characterization and Ligand-Enhanced Photo-Induced Color-Changing Behavior of Two Hydrogen-Bonded Ho(III)-Squarate Supramolecular Compounds

Two coordination polymers (CPs) with chemical formulas, [Ho(2)(C(4)O(4))(2)(C(2)O(4))(H(2)O)(8)]·4H(2)O (1) and [Ho(C(4)O(4))(1.5)(H(2)O)(3)] (2), (C(4)O(4)(2−) = dianion of squaric acid, C(2)O(4)(2−) = oxalate), have been synthesized and their structures were determined by single-crystal X-ray diffractometer (XRD). In compound 1, the coordination environment of Ho(III) ion is eight-coordinate bonded to eight oxygen atoms from two squarate, one oxalate ligands and four water molecules. The squarates and oxalates both act as bridging ligands with μ(1,2)-bis-monodentate and bis-chelating coordination modes, respectively, connecting the Ho(III) ions to form a one-dimensional (1D) ladder-like framework. Adjacent ladders are interlinked via O–H⋅⋅⋅O hydrogen bonding interaction to form a hydrogen-bonded two-dimensional (2D) layered framework and then arranged orderly in an AAA manner to construct its three-dimensional (3D) supramolecular architecture. In compound 2, the coordination geometry of Ho(III) is square-antiprismatic eight coordinate bonded to eight oxygen atoms from five squarate ligands and three water molecules. The squarates act as bridging ligands with two coordination modes, μ(1,2,3)-trismonodentate and μ(1,2)-bis-monodentate, connecting the Ho(III) ions to form a 2D bi-layered framework. Adjacent 2D frameworks are then parallel stacked in an AAA manner to construct its 3D supramolecular architecture. Hydrogen bonding interactions between the squarate ligands and coordinated water molecules in 1 and 2 both play important roles on the construction of their 3D supramolecular assembly. Compounds 1 and 2 both show remarkable ligand-enhanced photo-induced color-changing behavior, with their pink crystals immediately turning to yellow crystals under UV light illumination.