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Synthesis, Optical Properties, and Electronic Structures of Tetrakis(pentafluorophenyl)tetrathiaisophlorin Dioxide
Author(s) -
Mishra Vijay Lakshmi,
Furuyama Taniyuki,
Kobayashi Nagao,
Goto Kenta,
Miyazaki Takaaki,
Yang JyeShane,
Shinmyozu Teruo
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201505079
Subject(s) - chemistry , antiaromaticity , absorption spectroscopy , crystallography , alternation (linguistics) , dimethyldioxirane , bond length , absorption (acoustics) , electronic structure , photochemistry , crystal structure , molecule , computational chemistry , materials science , aromaticity , organic chemistry , linguistics , physics , philosophy , quantum mechanics , composite material
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 4 N ‐perimeter model and molecular orbital calculations, indicate that the broad band at λ =348 nm appears to contain N 2 and P 2 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 .