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Title: Phenalenyl-fused porphyrins with different ground states
Authors: Zeng W. 
Lee S.
Son M.
Ishida M.
Furukawa K.
Hu P. 
Sun Z.
Kim D.
Wu J. 
Keywords: Aromatic hydrocarbons
Physical properties
Polycyclic aromatic hydrocarbons
Hydrogen abstraction
Inert atmospheres
Intramolecular friedel-crafts
Organic electronics
Oxidative dehydrogenations
Porphyrin isomers
Spin distribution
Theoretical study
Ground state
Issue Date: 2015
Publisher: Royal Society of Chemistry
Citation: Zeng W., Lee S., Son M., Ishida M., Furukawa K., Hu P., Sun Z., Kim D., Wu J. (2015). Phenalenyl-fused porphyrins with different ground states. Chemical Science 6 (4) : 2427-2433. ScholarBank@NUS Repository.
Abstract: 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 1 and 2 were synthesized via an intramolecular Friedel-Crafts alkylation-followed-by oxidative dehydrogenation strategy. Our detailed experimental and theoretical studies revealed that 1 has a closed-shell structure with a small biradical character (y = 0.06 by DFT calculation) in the ground state, while 2 exists as a persistent triplet biradical at room temperature under inert atmosphere. Compound 1 underwent hydrogen abstraction from solvent during the crystal growing process while compound 2 was easily oxidized in air to give two dioxo-porphyrin isomers 11a/11b, which can be correlated to their unique biradical character and spin distribution. The physical properties of 1 and 2, their dihydro/tetrahydro-precursors 7/10, and the dioxo-compounds 11a/11b were investigated and compared. © 2015 The Royal Society of Chemistry.
Source Title: Chemical Science
ISSN: 20416520
DOI: 10.1039/c4sc03866e
Appears in Collections:Staff Publications

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