Insight into the Gd–Pt Bond: Slow Magnetic Relaxation of a Heterometallic Gd–Pt Complex

Abstract

Abstract Lanthanide (Ln) compounds are common research targets in the field of magnetism and optics. Their properties arise from the electrons localized in the f-orbital. Moreover, the effect of the covalency between lanthanide and ligands on magnetism has attracted significant attention. We have provided insight into the Gd–Pt bond (of the heterometallic Ln-Pt complexes: {[Pt(PhSAc)4]Ln[(PhSAc)4Pt]} NEt4·2DMF (Ln = Y(0), La(1), Gd(2); PhSAc = thiobenzoate, NEt4 = tetraethylammonium)); single-crystal polarized X-ray absorption near edge structure (XANES) reveal the electronic states around metal ion, where spectra of Gd-LIII edges show the Gd–Pt direction has the highest covalency (less ionic) around Gd ion in 2. In addition, calculating natural bonding (NBO) analysis, natural population analysis (NPA), LOL, and atoms in molecules (AIM), ab initio calculations reveal the role of metallic and organic ligands in the electronic and magnetic properties of Ln complexes. The slow magnetization relaxation of the Gd complex, which has not been reported previously in the Pt–Gd–Pt system, was observed up to 45 K, the highest temperature reported to date among isolated Gd-complexes (frequency range: 0.1–10000 Hz).