Temperature-dependent structural dynamics in covalent organic frameworks observed by cryogenic infrared spectroscopy

Understanding the structural dynamics of covalent organic frameworks (COFs) in response to external temperature change is necessary for these materials' application at cryogenic temperatures. Herein, we report reversible structural dynamics observed in covalent organic frameworks as the temperature varies from 298 K to 30 K. A series of frameworks (COF-300, COF-300-amine, and COF-V) was studied in situ using a cryogenic infrared spectroscopy system. We observed peak shifts in the Fourier-transform infrared (FTIR) spectrum of COFs as temperature cooled to 30 K, and these peak shifts were reversed as temperature returned to 298 K. Comparison of these materials showed different degrees of temperature-dependent change, through the quantitative degree of the peak shift and a qualitative description of which peaks shifted. A general IR peak shift towards a higher frequency as temperature decreased was observed, with COF-300 exhibiting quantitatively larger blue shifts in key vibrational modes as compared with the other frameworks. The nature of the conformational changes giving rise to the IR shifts was studied using quantum-chemistry calculations on model systems. The results of the calculations indicate that key peak shifts arise from a pedal motion experienced by the frameworks during cooling. This understanding of temperature-dependent framework dynamics will enhance the development, selection, and application of covalent organic frameworks at extreme temperatures.