Stable π Radical from a Contracted Doubly N-Confused Hexaphyrin by Double Palladium Metalation

Yutaka Hisamune; Keiichi Nishimura; Koji Isakari; Masatoshi Ishida; Shigeki Mori; Satoru Karasawa; Tatsuhisa Kato; Sangsu Lee; Dongho Kim; Hiroyuki Furuta

doi:10.1002/anie.201502285

Stable π Radical from a Contracted Doubly N-Confused Hexaphyrin by Double Palladium Metalation

Angew Chem Int Ed Engl. 2015 Jun 15;54(25):7323-7. doi: 10.1002/anie.201502285. Epub 2015 May 7.

Authors

Affiliations

¹ Department of Chemistry and Biochemistry, Graduate School of Engineering, and Education Center for Global Leaders in Molecular Systems for Devices, Kyushu University, Fukuoka 819-0395 (Japan).
² Integrated Center for Science, Ehime University, Matsuyama 790-8577 (Japan).
³ Graduate School of Pharmaceutical Sciences, Kyushu University, Fukuoka 812-8582 (Japan).
⁴ Institute for Liberal Arts and Sciences, Kyoto University, Kyoto 606-8501 (Japan).
⁵ Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749 (Korea).
⁶ Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749 (Korea). dongho@yonsei.ac.kr.
⁷ Department of Chemistry and Biochemistry, Graduate School of Engineering, and Education Center for Global Leaders in Molecular Systems for Devices, Kyushu University, Fukuoka 819-0395 (Japan). hfuruta@cstf.kyushu-u.ac.jp.

PMID: 25951535
DOI: 10.1002/anie.201502285

Abstract

A contracted doubly N-confused dioxohexaphyrin derivative served as a dinucleating metal ligand for unsymmetrical coordination. The complexation of two palladium(II) cations led to the formation of π-radical species that were persistent in atmospheric air in the presence of moisture. Effective delocalization of an unpaired electron over the hexaphyrin backbone could contribute to the distinct chemical stability.

Keywords: N-confusion; expanded porphyrins; palladium; stable radicals; two-photon absorption.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Cations / chemistry
Crystallography, X-Ray
Dimerization
Electrons
Ligands
Models, Molecular
Palladium / chemistry*
Porphyrins / chemistry*

Substances

Cations
Ligands
Porphyrins
Palladium