title: Möbius Aromatic [28]Hexaphyrin Germanium(IV) and Tin(IV) Complexes: Efficient Formation of Triplet Excited States.
abstract: [28]Hexaphyrin GeIVand SnIVcomplexes were synthesized in high yields by reactions of [28]hexaphyrin with GeCl4or SnCl4in the presence of triethylamine. Both complexes display distinct 28π Möbius aromatic character and possess a trigonal bipyramidal geometry at the central GeIVor SnIVatom. The equatorial hydroxy group of the GeIVcomplex was smoothly exchanged with neutral nucleophiles, such as phenol derivatives and thiophenol, with retention of configuration. In the SnIVcomplex, intersystem crossing to the T1state is remarkably enhanced owing to the effective heavy-atom effect, thus allowing the formation of the T1state in high yield. The T1states of the GeIVand SnVIcomplexes were found to be antiaromatic on the basis of the transient absorption features in line with the Baird rule.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto, 606-8502, Japan.
authors.forename: Mondo
authors.initials: M
authors.lastname: Izawa
authors.affiliation: Spectroscopy Laboratory for Functional π-Electronic, Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.
authors.forename: Taeyeon
authors.initials: T
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto, 606-8502, Japan.
authors.forename: Shin-Ichiro
authors.initials: SI
authors.lastname: Ishida
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto, 606-8502, Japan.
authors.forename: Takayuki
authors.initials: T
authors.lastname: Tanaka
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, 565-0871, Japan.
authors.forename: Tadashi
authors.initials: T
authors.lastname: Mori
authors.affiliation: Spectroscopy Laboratory for Functional π-Electronic, Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.
authors.forename: Dongho
authors.initials: D
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto, 606-8502, Japan.
authors.forename: Atsuhiro
authors.identifier: 0000-0001-8697-8488
authors.initials: A
authors.lastname: Osuka
keywords: Baird rule; Möbius aromaticity; chiral resolution; intersystem crossing; porphyrinoids