Synthesis, Optical Properties, and Electronic Structures of Tetrakis(pentafluorophenyl)tetrathiaisophlorin Dioxide
Journal
Chemistry - A European Journal
Journal Volume
22
Journal Issue
27
Pages
9190-9197
Date Issued
2016
Author(s)
Abstract
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 �f =348 and 276 nm, with a weak tail that extends to �f ?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 �f =348 nm appears to contain N 2 and P 2 bands, and 12 is classified as a 4n�k 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 .
SDGs
Type
journal article