A meso–meso β-β β-β triply linked subporphyrin dimer 6 was synthesized by stepwise reductive elimination of β-to-β doubly PtII-bridged subporphyrin dimer 9. Dimer 6 was characterized by spectroscopic and electrochemical measurements, theoretical calculations, and picosecond time-resolved transient absorption spectroscopy. X-ray diffraction analysis reveals that 6 has a bowl-shaped structure with a positive Gaussian curvature. Despite the curved structure, 6 exhibits a remarkably red-shifted absorption band at 942 nm and a small electrochemical HOMO–LUMO gap (1.35 eV), indicating an effectively conjugated π-electronic network.
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The work in Kyoto was supported by Grants-in-Aid from JSPS (Nos.: 25220802 (Scientific Research (S)), 16K13952 (Exploratory Research). N.F. acknowledges a JSPS Fellowship for Young Scientists. The work in Yonsei was supported by the Global Research Laboratory (GRL) Program funded by the Ministry of Science, ICT & Future, Korea (2013K1A1A2A02050183).
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