Excited State Transient Phenomena in Two Different Phases of the Photoactive MOF MIP‐177(Ti)

Abstract The metal organic framework (MOF) MIP‐177(Ti) is under the spotlight for its robust photo‐response and stability. This MOF can be synthesized in forms: MIP‐177(Ti)‐LT (LT: low temperature) and MIP‐177(Ti)‐HT (HT: high temperature). The MIP‐177(Ti)‐LT version comprises of Ti 12 O 15 units interconnected by 3,3′,5,5′‐tetracarboxydiphenylmethane (mdip) ligands and interconnecting formate groups. Upon high temperature treatment, MIP‐177(Ti)‐LT loses its formate groups, thus rearranging into a continuous 1‐D chain of Ti 6 O 9 units leading to the MIP‐177(Ti)‐HT. Based on this 1‐D connected structure, one should expect a higher catalytic activity of MIP‐177(Ti)‐HT. Nevertheless, the hydrogen evolution reaction photoactivity assessment clearly indicates the opposite. Combining transient IR measurements (TRIR), TAS and DFT/TD‐DFPT calculations unveils the reasons for this situation. The TRIR measurements evidence that the photoinduced electrons are located in the inorganic part, while the holes are in the mdip ligand. The longer lifetime of MIP‐177(Ti)‐LT is mapped onto a slower decay of the Ti–O related peaks. A reversible change in the coordination of the carboxylate groups from a bidentate to a monodentate coordination is observed only in MIP‐177(Ti)‐LT. Complementary DFT and TD‐DFPT simulations demonstrate a higher electron delocalization on the inorganic part for MIP‐177(Ti)‐LT (hence, enhanced mobility and slower recombination), thus explaining its superior photocatalytic activity.