Water Sorption Controls Extreme Single-Crystal-to-Single-Crystal Molecular Reorganization in Hydrogen Bonded Organic Frameworks

Abstract

As hydrogen bonded frameworks are held together by relatively weak interactions, they often form several different frameworks under slightly different synthesis conditions and respond dynamically to stimuli such as heat and vacuum. However, these dynamic restructuring processes are often poorly understood. In this work, three isoreticular hydrogen bonded organic frameworks assembled through charge-assisted amidinium···carboxylate hydrogen bonds (1C/C, 1Si/C and 1Si/Si) are studied. Three distinct phases for 1C/C and four for 1Si/C and 1Si/Si are fully structurally characterized. The transitions between these phases involve extreme yet recoverable molecular-level framework reorganization. It is demonstrated that these transformations are related to water content and can be controlled by humidity, and that the nonporous anhydrous phase of 1C/C shows reversible water sorption through single crystal to crystal restructuring. This mechanistic insight opens the way for the future use of the inherent dynamism present in hydrogen bonded frameworks.