N-Confused Hexapyrrolic Phlorinoid with NIR Absorption: Synthesis, Fusion, Oxidation, and Copper(II) Coordination

Yu Du; Bin Zhu; Qizhao Li; Glib Baryshnikov; Chuanwan Wei; Yingwu Lin; Guangxian Su; Chengjie Li; Hans Ågren; Yongshu Xie

doi:10.1021/acs.orglett.0c03710

N-Confused Hexapyrrolic Phlorinoid with NIR Absorption: Synthesis, Fusion, Oxidation, and Copper(II) Coordination

Org Lett. 2020 Dec 18;22(24):9648-9652. doi: 10.1021/acs.orglett.0c03710. Epub 2020 Dec 9.

Authors

Yu Du¹, Bin Zhu¹, Qizhao Li^{1

2}, Glib Baryshnikov³, Chuanwan Wei⁴, Yingwu Lin⁴, Guangxian Su¹, Chengjie Li¹, Hans Ågren³, Yongshu Xie¹

Affiliations

¹ Key Laboratory for Advanced Materials and Institute of Fine Chemicals, Shanghai Key Laboratory of Functional Materials Chemistry, School of Chemistry & Molecular Engineering, State Key Laboratory of Bioreactor Engineering, Laboratory of Pharmaceutical Crystal Engineering & Technology, School of Pharmacy, East China University of Science & Technology, 200237, Shanghai, China.
² Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, Hunan Normal University, 410081, Changsha, China.
³ Key Department of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology, SE-10691, Stockholm, Sweden.
⁴ School of Chemistry and Chemical Engineering, University of South China, 421001, Hengyang, China.

PMID: 33295779
DOI: 10.1021/acs.orglett.0c03710

Abstract

An N-confused hexapyrrolic phlorinoid 1 and its isomer N-fused hexapyrrolic phlorinoid 2 were synthesized through [4 + 2] condensation. Both 1 and 2 can be readily transformed into N-confused hexapyrrolic phlorinone 3 under aerobic conditions. Coordination of 1 with Cu(acac)₂ afforded two different mono-Cu(II) complexes 4 and 5 with CNNN and ONNN coordination environments, respectively. The NIR absorption bands can be effectively modulated up to 1265 nm through the oxidation, fusion, and metalation reactions.