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Issue 4, 2015
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Phenalenyl-fused porphyrins with different ground states

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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.

Graphical abstract: Phenalenyl-fused porphyrins with different ground states

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Supplementary files

Article information


Submitted
13 Dec 2014
Accepted
03 Feb 2015
First published
04 Feb 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 2427-2433
Article type
Edge Article

Phenalenyl-fused porphyrins with different ground states

W. Zeng, S. Lee, M. Son, M. Ishida, K. Furukawa, P. Hu, Z. Sun, D. Kim and J. Wu, Chem. Sci., 2015, 6, 2427
DOI: 10.1039/C4SC03866E

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