A meso–meso β‐β β‐β Triply Linked Subporphyrin Dimer. Issue 40 (23rd August 2017)

• Record Type: Journal Article
• Authors: Okuda, Yasuhiro; Fukui, Norihito; Kim, Jinseok; Kim, Taeyeon; Jiang, Hua‐Wei; Copley, Graeme; Kitano, Masaaki; Kim, Dongho; Osuka, Atsuhiro
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 40(2017)
• Page Start: 12317
• Page End: 12321
• Publication Date: 2017-08-23
• Subjects: curved structures -- fused porphyrinoids -- near-IR absorption -- positive Gaussian curvature -- subporphyrin; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201707123
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A meso–meso β‐β β‐β triply linked subporphyrin dimer6 was synthesized by stepwise reductive elimination of β‐to‐β doubly Pt II ‐bridged subporphyrin dimer9 . Dimer6 was characterized by spectroscopic and electrochemical measurements, theoretical calculations, and picosecond time‐resolved transient absorption spectroscopy. X‐ray diffraction analysis reveals that6 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. Abstract : A triply linked subporphyrin dimer was synthesized by stepwise reductive elimination of a β‐to‐β doubly Pt II ‐bridged subporphyrin dimer with the concurrent formation of the meso–meso bond. Despite the curved structure, the triply linked dimer displayed a remarkably red‐shifted absorption spectrum and narrow electrochemical HOMO–LUMO gap because of the effectively conjugated π‐electronic network.