Ferromagnetically Coupled Copper(II) Clusters Incorporated in Functionalized Boltorn H30 Hyperbranched Polymer Architecture: ESR, Magnetic Susceptibility Measurements, and Quantum-Chemical Calculations

The unusual temperature behavior of the electron spin resonance (ESR) spectra and magnetic properties are experimentally observed in copper­(II) complexes with a dendritic ligand based on the Boltorn H30 polymer (Perstorp Specialty Chemicals AB, Sweden) functionalized with fumaric acid residues in a molar ratio of 1:6. The ESR spectra at low temperatures show signs of transition to higher spin states at temperatures below 8–10 K, and the temperature dependences of the integral ESR signal intensities and magnetic susceptibility show the positive deviation from the Curie–Weiss law, thereby pointing to the presence of ferromagnetic exchange interactions in the system under study. The values of the exchange interaction parameters are calculated by quantum-chemical simulation of the possible structure of the copper­(II) complex when assuming the formation of trinuclear coordination sites embedded in the hyperbranched polymer structure. The results of density functional theory calculations indicate the possibility of ferromagnetic exchange through carboxylate bridges in the trinuclear magnetic clusters, and the calculated values of the exchange interaction parameters make it possible to construct theoretical curves of the temperature dependence of the effective magnetic moment, which satisfactorily fit the experimental data, especially considering that polymers are characterized by disperse molecular weights and chemical structures.