A meso-meso β-β β-β Triply Linked Subporphyrin Dimer

Yasuhiro Okuda; Norihito Fukui; Jinseok Kim; Taeyeon Kim; Hua-Wei Jiang; Graeme Copley; Masaaki Kitano; Dongho Kim; Atsuhiro Osuka

doi:10.1002/anie.201707123

A meso-meso β-β β-β Triply Linked Subporphyrin Dimer

Angew Chem Int Ed Engl. 2017 Sep 25;56(40):12317-12321. doi: 10.1002/anie.201707123. Epub 2017 Aug 23.

Authors

Yasuhiro Okuda¹, Norihito Fukui¹, Jinseok Kim², Taeyeon Kim², Hua-Wei Jiang¹, Graeme Copley¹, Masaaki Kitano¹, Dongho Kim², Atsuhiro Osuka¹

Affiliations

¹ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
² Spectroscopy Laboratory of Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.

PMID: 28744951
DOI: 10.1002/anie.201707123

Abstract

A meso-meso β-β β-β triply linked subporphyrin dimer 6 was synthesized by stepwise reductive elimination of β-to-β doubly Pt^II -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.

Keywords: curved structures; fused porphyrinoids; near-IR absorption; positive Gaussian curvature; subporphyrin.

Publication types

Research Support, Non-U.S. Gov't