Issue 4, 2015

Phenalenyl-fused porphyrins with different ground states

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

Supplementary files

Article information

Article type
Edge Article
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
Creative Commons BY license

Chem. Sci., 2015,6, 2427-2433

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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