3 years ago

Hetero Face-to-Face Porphyrin Array with Cooperative Effects of Coordination and Host–Guest Complexation

Hetero Face-to-Face Porphyrin Array with Cooperative Effects of Coordination and Host–Guest Complexation
Jun Terao, Yasuhiro Tachibana, Maning Liu, Yasushi Tsuji, Yusuke Chiba, Tetsuaki Fujihara
We successfully synthesized a hetero face-to-face porphyrin array composed of ZnTPP and RuTPP(DABCO)2 (TPP: 5, 10, 15, 20-tetraphenylporphyrin, DABCO: 1,4-diazabi-cyclo[2.2.2]octane) in 2:1 molar ratio. A cyclic Zn porphyrin dimer (ZnCP) was also used as the host molecule for the Ru porphyrin. In the latter, the Ru-DABCO bonding in RuTPP(DABCO)2 was stabilized by the host-guest complexation. Reaction progress kinetic analysis of the ligand substitution reaction of RuTPP(DABCO)2 and that in ZnCP revealed the stabilization mechanism of the Ru-DABCO bonding. Photoinduced electron transfer (PET) from the Zn porphyrin to the Ru porphyrin was observed in the porphyrin array. The host-guest stabilization of unstable complex for construction of a donor—acceptor–donor structure is expected to be a new method for an artificial photosynthesis. Not Harvey Dent: Two face-to-face type porphyrin arrays with Zn porphyrin, one of the promising units for artificial photosynthesis, have been synthesized using RuTPP(DABCO)2 (TPP: 5, 10, 15, 20-tetraphenylporphyrin, DABCO: 1,4-diazabi-cyclo[2.2.2]octane). The unstable Ru-DABCO bonding in RuTPP(DABCO)2 was stabilized by a Zn cyclic porphyrin dimer through host–guest complexation. The host-guest stabilization of unstable complex for construction of a donor—acceptor–donor structure could be a new method for artificial photosynthesis.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/asia.201700738

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