Metal

Catalysis

Adsorption

Polymer chemistry

Photochemistry

Materials science

Benzaldehyde

Receptor

Biochemistry

Computer science

Titanium

Inorganic chemistry

Benzyl alcohol

Alkoxide

Singlet oxygen

Ligand (biochemistry)

Organic chemistry

Porphyrin

Oxygen

Cluster (spacecraft)

Carboxylate

Metal-organic framework

Hydrolysis

Composite material

Crystallography

Chemistry

Programming language

Photocatalysis

Crystallinity

Angewandte Chemie International Edition

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 Ti 4+ 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., 1957.3 m 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 ( 1 O 2 ) and superoxide ( . O 2 − ) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde.

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