Effect of Geometrical Distortion on the Electronic Structure: Synthesis and Characterization of Monoradical-Coordinated Mononuclear Cu(II) Complexes

Inorganic Chemistry
Samir GhoraiChandan Mukherjee

Abstract

Ligand H3Sami(Mixed(tBu)) was composed of two different compartments, a redox-active 2-aminophenol and a salen salicylidene. Both compartments were linked via a benzyl linker. The ligand reacted with CuCl2·2H2O under air in the presence of Et3N and provided the corresponding monoradical-coordinated mononuclear Cu(II) complex (1). Complex 1, in solution, reacted with air and provided complex 2 via ligand-centered oxygenation at the benzyl-CH2 position. Both complexes were characterized via IR, mass spectrometry, X-ray single-crystal diffraction, variable-temperature magnetic susceptibility, cyclic voltammograms (CVs), and UV-vis/NIR spectroscopic techniques. X-ray crystallographic analyses clearly showed almost equally distorted square planar geometry around the Cu(II) atom in both complexes. However, the bending of the radical-containing C6 ring compared to the N1-Cu1-O1 plane was different in both complexes. While complex 1 was paramagnetic and showed a ferromagnetic coupling between the dx(2)-y(2) magnetic orbital of Cu(II) ion and the pz orbital of coordinated π-radical, complex 2 was diamagnetic by experiencing a strong antiferromagnetic coupling between the two magnetic orbitals. UV-vis/NIR spectra of the complexes were do...Continue Reading

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Citations

Aug 11, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Manas Kumar Mondal, Chandan Mukherjee
Sep 13, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Prasenjit Sarkar, Chandan Mukherjee
Jan 16, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Amit RajputRabindranath Mukherjee
Nov 16, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Sridhar BanerjeeTapan Kanti Paine

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