A single crystalline porphyrinic titanium metal–organic framework† †Electronic supplementary information (ESI) available. CCDC [1036868]. For ESI and crystallographic data in CIF or other electronic format. See DOI: 10.1039/c5sc00916b Click here for additional data file. Click here for additional data file.

We successfully assembled the photocatalytic titanium-oxo cluster and photosensitizing porphyrinic linker into a metal–organic framework (MOF), namely PCN-22. A preformed titanium-oxo carboxylate cluster is adopted as the starting material to judiciously control the MOF growth process to afford single crystals. This synthetic method is useful to obtain highly crystalline titanium MOFs, which has been a daunting challenge in this field. Moreover, PCN-22 demonstrated permanent porosity and photocatalytic activities toward alcohol oxidation.