Competition of Hydrogen Bonds and Coordinate Bonds Induces a Reversible Crystal Transformation.

Abstract

Achieving reversible molecular crystal transformation between coordinate aggregates and hydrogen bonded assemblies has been a challenging task because coordinate bonds are generally much stronger than hydrogen bonds. Recently, we have reported the incorporation of silver ions into the cyanuric acid-melamine (CAM) network, resulting in the formation of a 1D coordination polymer (crystal 1) through forming the κ1N-Ag-κ2N coordination bonds. In this work, we find crystal 1 will undergo reversible transformation to hydrogen bonded coordinate units (crystal 2) through the breaking of coordinate chains and then the addition of CAM hydrogen bonding motifs into the framework. Crystal 2 presents a pseudohexagonal arrangement comprised of the κ1N-Ag-κ2N units connected by two sets of the triple hydrogen bonds, which extends two-dimensionally and stacks into a layer-structured crystal. Light was shed on the tautomerization of CA and M ligands associated with the crystal transformations using single crystal X-ray diffraction and infrared spectroscopy by analyzing the bond lengths and vibrations. We also highlight that photoluminescence can be a useful tool to probe the tautomer conversions of conjugated molecules. Furthermore, crystal 1 demonstrates high flexibility and can be bent over 180° and recover to its original shape after stress release. Crystal 2, on the contrary, is brittle and shows distinct mechanical anisotropy along different crystal orientations, as unveiled by nanoindentation measurements. The elastic modulus is well correlated with the chemical bonding strength along each orientation, and it is noteworthy that the contribution of the triple hydrogen bonds is comparable to that of the coordination bonds.