Phenalenyl-fused porphyrins with different ground states

Materials based on biradicals/biradicaloids have potential applications for organic electronics, photonics and spintronics. In this work, we demonstrated that hybridization of porphyrin and polycyclic aromatic hydrocarbon could lead to a new type of stable biradicals/biradicaloids with tunable groun...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2015-04, Vol.6 (4), p.2427-2433
Main Authors: Zeng, Wangdong, Lee, Sangsu, Son, Minjung, Ishida, Masatoshi, Furukawa, Ko, Hu, Pan, Sun, Zhe, Kim, Dongho, Wu, Jishan
Format: Article
Language:English
Subjects:
Chemistry
Crystals
Electronics
Ground state
Isomers
Mathematical analysis
Physical properties
Porphyrins
Strategy
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Summary:Materials based on biradicals/biradicaloids have potential applications for organic electronics, photonics and spintronics. In this work, we demonstrated that hybridization of porphyrin and polycyclic aromatic hydrocarbon could lead to a new type of stable biradicals/biradicaloids with tunable ground state and physical property. Mono- and bis-phenalenyl fused porphyrins and were synthesized an intramolecular Friedel-Crafts alkylation-followed-by oxidative dehydrogenation strategy. Our detailed experimental and theoretical studies revealed that has a closed-shell structure with a small biradical character ( = 0.06 by DFT calculation) in the ground state, while exists as a persistent triplet biradical at room temperature under inert atmosphere. Compound underwent hydrogen abstraction from solvent during the crystal growing process while compound was easily oxidized in air to give two dioxo-porphyrin isomers / , which can be correlated to their unique biradical character and spin distribution. The physical properties of and , their dihydro/tetrahydro-precursors / , and the dioxo-compounds / were investigated and compared.
ISSN:2041-6520
2041-6539
DOI:10.1039/c4sc03866e