Conformational Locking by Design: Relating Strain Energy with Luminescence and Stability in Rigid Metal–Organic Frameworks

Minimization of the torsional barrier for phenyl ring flipping in a metal–organic framework (MOF) based on the new ethynyl-extended octacarboxylate ligand H<sub>8</sub>TDPEPE leads to a fluorescent material with a near-dark state. Immobilization of the ligand in the rigid structure also unexpectedly causes significant strain. We used DFT calculations to estimate the ligand strain energies in our and all other topologically related materials and correlated these with empirical structural descriptors to derive general rules for trapping molecules in high-energy conformations within MOFs. These studies portend possible applications of MOFs for studying fundamental concepts related to conformational locking and its effects on molecular reactivity and chromophore photophysics.