Synthesis,Optical Properties,and Electronic Structures of Tetrakis(pentafluorophenyl)tetrathiaisophlorin Dioxide |
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| Authors: | Dr Vijay Lakshmi Mishra Prof Taniyuki Furuyama Prof Nagao Kobayashi Prof Kenta Goto Dr Takaaki Miyazaki Prof Jye‐Shane Yang Prof Teruo Shinmyozu |
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| Institution: | 1. Institute for Materials Chemistry and Engineering (IMCE), Kyushu University, Fukuoka, Japan;2. Department of Chemistry, Graduate School of Sciences, Kyushu University, Fukuoka, Japan;3. Institute for Chemical Research, Kyoto University, Uji, Japan;4. Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Japan;5. Faculty of Textile Science and Technology, Shinshu University, Tokida, Ueda, Japan;6. Institute of Chemistry, Academia Sinica, No. 128, Nankang, Taipei, Taiwan;7. Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Taipei, Taiwan |
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| 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 1H NMR spectroscopy data indicate that 12 has more antiaromatic character than 11 . |
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| Keywords: | absorption heterocycles isophlorins porphyrinoids synthesis design |
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