A Directly Fused Subporphyrin Dimer with a Wavelike Structure. Issue 32 (21st June 2016)

• Record Type: Journal Article
• Authors: Okuda, Yasuhiro; Tsurumaki, Eiji; Oh, Juwon; Sung, Jooyoung; Kim, Dongho; Osuka, Atsuhiro
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 32(2016)
• Page Start: 9212
• Page End: 9215
• Publication Date: 2016-06-21
• Subjects: density functional calculations -- dimerization -- iridium -- porphyrinoids -- X-ray diffraction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201603759
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: [Ni(cod)2 ]‐mediated intramolecular reductive coupling of β–β′ linked meso, meso′‐dibromosubporphyrin dimer gave the anti ‐isomer of meso–meso′, β–β′ doubly linked subporphyrin dimer as the first example of a fused subporphyrin dimer. The fused dimer3 anti displays an wavelike coplanar structure, a perturbed and red‐shifted absorption spectrum, reversible redox behaviors with a decreased electrochemical HOMO–LUMO band gap, and a short S1 ‐state lifetime owing to the delocalized π‐electronic network. Abstract : Link up : [Ni(cod)2 ]‐mediated intramolecular reductive coupling of a β – β ′ linked meso, meso′‐dibromosubporphyrin dimer gave the anti ‐isomer of a fused subporphyrin dimer. The new dimer displays a wavelike coplanar structure, a perturbed and red‐shifted absorption spectrum, reversible redox behaviors with a decreased electrochemical HOMO–LUMO band gap, and a shortened S1 ‐state lifetime owing to the effective conjugation through fusion.