A metal-organic tetrahedron as a redox vehicle to encapsulate organic dyes for photocatalytic proton reduction.
The design of artificial systems that mimic highly evolved and finely tuned natural photosynthetic systems is a subject of intensive research. We report herein a new approach to constructing supramolecular systems for the photocatalytic generation of hydrogen from water by encapsulating an organic dye molecule into the pocket of a redox-active metal-organic polyhedron. The assembled neutral Co4L4 tetrahedron consists of four ligands and four cobalt ions that connect together in alternating fashion. The cobalt ions are coordinated by three thiosemicarbazone NS chelators and exhibit a redox potential suitable for electrochemical proton reduction. The close proximity between the redox site and the photosensitizer encapsulated in the pocket enables photoinduced electron transfer from the excited state of the photosensitizer to the cobalt-based catalytic sites via a powerful pseudo-intramolecular pathway. The modified supramolecular system exhibits TON values comparable to the highest values reported for related cobalt/fluorescein systems. Control experiments based on a smaller tetrahedral analogue of the vehicle with a filled pocket and a mononuclear compound resembling the cobalt corner of the tetrahedron suggest an enzymatic dynamics behavior. The new, well-elucidated reaction pathways and the increased molarity of the reaction within the confined space render these supramolecular systems superior to other relevant systems.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China.
Xu
X
Jing
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China.
Cheng
C
He
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China.
Yang
Y
Yang
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China.
Chunying
C
Duan
D003035:Cobalt; D004396:Coloring Agents / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009930:Organic Chemicals; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D010788:Photosynthesis
D004396:Coloring Agents; D009930:Organic Chemicals; D003035:Cobalt