Copper(ii) and zinc(ii) complexation with N-ethylene hydroxycyclams and consequences on the macrocyclic backbone configuration. Issue 22 (26th May 2022)

• Record Type: Journal Article
• Authors: AlHaddad, Nancy; Lelong, Evan; Suh, Jong-Min; Cordier, Marie; Lim, Mi Hee; Royal, Guy; Platas-Iglesias, Carlos; Bernard, Hélène; Tripier, Raphaël
• Is Part Of: Dalton transactions. Volume 51:Issue 22(2022)
• Page Start: 8640
• Page End: 8656
• Publication Date: 2022-05-26
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt00941b
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : We report a series of four cyclams and cross-bridged cyclams, N -functionalized by one hydroxyethyl arm, which may incorporate additional methyl(s) group(s). Abstract : We report a series of four cyclams and cross-bridged cyclams, N -functionalized by one hydroxyethyl arm, which may incorporate additional methyl(s) group(s). The Cu(ii ) and Zn(ii ) complexes of these ligands were synthesized and fully characterized. The investigation of the metal complexes in solid-state and in solution was carried via X-ray diffraction, NMR, EPR, absorption spectroscopy and DFT calculations. The influence of N -functionalization on their structural/stereochemical properties, electrochemical behavior and kinetic inertness was carefully studied and identified. N -Functionalization by a hydroxyethyl group did not influence importantly the stereochemical properties of the complexes. However, it stabilized the complexes kinetically and electrochemically. As for N -methylation, it induces significant distortion of the coordination geometry, decreasing the kinetic inertness of the complexes and stabilizing Cu + . Overall, this work expanded the family of cyclam and cross-bridged cyclam metal complexes and provides a detailed analysis of their structural features. The rather large body of data accumulated for this family of complexes provides opportunities to design systems with pre-determined properties for specific applications.