Phenalenyl-fused Porphyrins with Different Ground States

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 Aug 30

PMID 30154998

Citations 4

Authors

Wangdong Zeng

Sangsu Lee

Minjung Son

Masatoshi Ishida

Ko Furukawa

Pan Hu

Zhe Sun

Dongho Kim

Jishan Wu

Affiliations

Soon will be listed here.

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 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.

Citing Articles

Magnetic Interplay between π-Electrons of Open-Shell Porphyrins and d-Electrons of Their Central Transition Metal Ions.

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Carbene derived diradicaloids - building blocks for singlet fission?.

Messelberger J, Grunwald A, Pinter P, Hansmann M, Munz D Chem Sci. 2018; 9(28):6107-6117.

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Porphyrinoids as a platform of stable radicals.

Shimizu D, Osuka A Chem Sci. 2018; 9(6):1408-1423.

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Highly planar diarylamine-fused porphyrins and their remarkably stable radical cations.

Fukui N, Cha W, Shimizu D, Oh J, Furukawa K, Yorimitsu H Chem Sci. 2017; 8(1):189-199.

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