Solvent-regulated assemblies and guest-adsorption properties of Ag(I) coordination polymers with p-phenylenediacetonitrile

Three unique complexes with diverse coordination architectures were synthesized upon complexation of p-phenylenediacetonitrile with silver trifluoroacetate in response to regulation of solvents system. Crystallization from benzene and m-xylene yield two 2D layered frameworks 1 and 2, respectively, of which 1 contains benzene as guest but 2 does not. In 1, every two ligands double link two 1D chains in trans fashion while each ligand is μ2-bridged to two 1D chains in 2. This difference in coordination can be properly assigned to the significant solvent steric effect on assembled reactions, which ultimately leads to two types of pores with different size and shape formed within the 2D structure of 1 and 2, respectively. 3 was recrystallized of guest-eliminated 1a from DMSO and share the same chemical formula with 1a, yet differ greatly in coordination topology, demonstrating the solvent-mediated crystallization and phase transition. The benzenes in 1 could be liberated accompanying the observable distortion of its framework as evidenced by XRPD. The guest-eliminated 1a declined the reincorporation of aromatic guests such as benzene, toluene and xylene isomers due to the probable shrinkage of pores in 1a, but accommodated those smaller guests such as water, methanol and ethanol.