Phenoxazinyl Zn(II) diradical complex formed via redox-driven cyclization of a 2-aminophenol-based N3O ligand. Isolation of the modified N3 ligand radical and its Ni(II) complex

Narottam Mukhopadhyay; Arunava Sengupta; Francesc Lloret; Rabindranath Mukherjee

doi:10.1039/d4dt00374h

Phenoxazinyl Zn(II) diradical complex formed via redox-driven cyclization of a 2-aminophenol-based N₃O ligand. Isolation of the modified N₃ ligand radical and its Ni(II) complex

Dalton Trans. 2024 Apr 16;53(15):6515-6519. doi: 10.1039/d4dt00374h.

Authors

Narottam Mukhopadhyay¹, Arunava Sengupta², Francesc Lloret³, Rabindranath Mukherjee⁴

Affiliations

¹ Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, West Bengal 741246, India.
² Department of Chemistry & Chemical Biology, Indian Institute of Technology (ISM) Dhanbad, Jharkhand 826004, India.
³ Department de Química Inorgànica/Instituto de Ciencia Molecular (ICMOL), Universitat de València, Polígono de la Coma, s/n, 46980 Paterna, València, Spain.
⁴ Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India. rnm@iitk.ac.in.

PMID: 38563205
DOI: 10.1039/d4dt00374h

Abstract

Aerobic reaction between the pyridine-2-carboxamide-2-aminophenol N₃O ligand (H₃L¹) and Zn(ClO₄)₂·6H₂O in CH₃CN affords an N₃ phenoxazinylate coordinated Zn(II) complex; its diradical electronic structure [Zn^II{(L¹*)˙^-}₂] has been elucidated from redox, spectroscopic (UV-VIS and EPR), and magnetic measurements and DFT calculations. Isolation and characterization of the metal-assisted redox-driven modified N₃ ligand as a radical cation (H₂L¹*)˙⁺ and its Ni(II)-diradical complex [Ni^II{(L¹*)˙^-}₂] have also been achieved.