title: Synthesis, Optical Properties, and Electronic Structures of Tetrakis(pentafluorophenyl)tetrathiaisophlorin Dioxide.
abstract: The synthesis, structure, optical and redox properties, and electronic structure of tetrakis(pentafluorophenyl)tetrathiaisophlorin dioxide (12) are reported. Oxidation of tetrakis(pentafluorophenyl)tetrathiaisophlorin (11) with dimethyldioxirane afforded the oxidized product, which was the tetrathiaisophlorin with two thiophene 1-oxide moieties (12). More significant nonplanarity and greater bond length alternation in 12 than those of 11 were observed by X-ray structural analysis. The absorption spectrum of 12 contains two bands at λ=348 and 276 nm, with a weak tail that extends to λ≈650 nm. Analysis of the magnetic circular dichroism spectrum of 12, based on Michl's 4N-perimeter model and molecular orbital calculations, indicate that the broad band at λ=348 nm appears to contain N2 and P2 bands, and 12 is classified as a 4nπ system, similar to 11. The nuclear-independent chemical shift values and (1) H NMR spectroscopy data indicate that 12 has more antiaromatic character than 11.
authors.affiliation: Institute for Materials Chemistry and Engineering (IMCE), Kyushu University, Fukuoka, 819-0395, Japan.|Department of Chemistry, Graduate School of Sciences, Kyushu University, Fukuoka, 819-0395, Japan.|Institute for Chemical Research, Kyoto University, Uji, 611-0011, Japan.
authors.forename: Vijay Lakshmi
authors.initials: VL
authors.lastname: Mishra
authors.affiliation: Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.
authors.forename: Taniyuki
authors.initials: T
authors.lastname: Furuyama
authors.affiliation: Faculty of Textile Science and Technology, Shinshu University, Tokida, Ueda, 386-0018, Japan.
authors.forename: Nagao
authors.initials: N
authors.lastname: Kobayashi
authors.affiliation: Institute for Materials Chemistry and Engineering (IMCE), Kyushu University, Fukuoka, 819-0395, Japan. vijayam.vns@gmail.com.
authors.forename: Kenta
authors.initials: K
authors.lastname: Goto
authors.affiliation: Institute of Chemistry, Academia Sinica, No. 128, Academia Road Sec. 2, Nankang, Taipei, 11529, Taiwan.
authors.forename: Takaaki
authors.initials: T
authors.lastname: Miyazaki
authors.affiliation: Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei, 10617, Taiwan.
authors.forename: Jye-Shane
authors.initials: JS
authors.lastname: Yang
authors.affiliation: Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei, 10617, Taiwan. tshinmyozu@ntu.edu.tw.
authors.forename: Teruo
authors.initials: T
authors.lastname: Shinmyozu
keywords: absorption; heterocycles; isophlorins; porphyrinoids; synthesis design