Titanium-Carboxylate Metal-Organic Framework Based on an Unprecedented Ti-Oxo Chain Cluster

Titanium(IV)-based metal-organic frameworks (Ti-MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single-crystalline Ti-carboxylate MOF (DGIST-1) composed of an unprecedented Ti-oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4-carboxyphenyl)porphyrin). Preformed Ti-oxo clusters were used as Ti4+ sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti-alkoxide precursors, thus, enabling the formation of the highly crystalline Ti-MOF. The successfully activated DGIST-1 exhibited a higher surface area (i.e., 1957.3m(2)g(-1)) than previously reported Ti-MOFs due to its high crystallinity. Furthermore, the visible-light-responsive photocatalytic activity of DGIST-1 was confirmed by the simultaneous generation of singlet oxygen (O-1(2)) and superoxide (O-.(2)-) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde.