Water Content-Controlled Formation and Transformation of Concomitant Pseudopolymorph Coordination Polymers

[Image: see text] Two concomitant pseudopolymorph coordination polymers {[Cd(2)L(2)(OAc)(4)]·2DMSO}(n) (1) and {[CdL(OAc)(2)]·2.75H(2)O}(n) (2) were synthesized by self-assembly of 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (L) and cadmium acetate in DMSO. Single-crystal X-ray diffraction confirmed that 1D ladder structural motifs exist for pseudopolymorphs 1 and 2 which contain DMSO and water guest molecules, respectively. Our study illustrated the active role of solvent water content in obtaining compound 2. We find that the presence of water as an impurity in the DMSO solvent creates the possibility of formation of concomitant pseudopolymorph coordination polymers which is a unique event. Furthermore, our analyses showed the effect of environmental humidity on the transformation of unstable compound 1. 1D ladder pseudopolymorphic compound 1 could be transformed to guest-free 1D linear compound [CdL(OAc)(2)(H(2)O)](n) (3′) (the powder form of single crystals of 3) through a scarce case of water absorption from air. Also, the crystalline material of coordination polymer 3 was transformed to coordination polymer 2 through the dissolution–recrystallization structural transformation process in DMF or DMSO. Our study clarified that the amount of water in the reaction container can control the formation of one of the compounds 2 or 3. In the presence of a significant amount of water, compound 3 (coordinated water) will be produced, whereas if a small amount of water is present, compound 2 (uncoordinated water) is prepared as an exclusive product.