Air-Stable Gadolinium Precursors for the Facile Microwave-Assisted Synthesis of Gd₂O₃ Nanocontrast Agents for Magnetic Resonance Imaging

Using metal organic precursors in materials synthesis remains a challenge due to their high moisture susceptibility. In this work, we describe a facile methodology for the synthesis of Gd2O3-based contrast agents from two new gadolinium-based complexes. [Gd(PyTFP)(4)] (PyH) 1 (PyTFP = C8H5NOF3, Py = C5H5N) and [Gd(DMOTFP)(3)Py] 2 (DMOTFP = C8H7NO2F3) were synthesized via a classical ligand exchange reaction of [Gd{N(SiMe3)(2)}(3)] under inert conditions. As a result, X-ray diffraction analysis revealed a distorted square antiprismatic coordination and an augmented triangular prismatic arrangement of ligands around gadolinium atoms in 1 and 2, respectively. It also showed that 1 is an anionic complex of formula [Gd(PyTFP)(4)](PyH), while a neutral tris-compound, [Gd(DMOTFP)(3)Py], was obtained as a pyridine adduct in 2. Fast and reproducible microwave-assisted decomposition of 1 and 2 provided homogeneous Gd(OH)(3) nanorods at mild temperature without using any surfactant or capping reagent. As-synthesized nanorods were easily transformed into a cubic phase of Gd2O3 nanoparticles by thermal treatment under ambient conditions. The magnetic measurement showed the typical paramagnetic behavior of the Gd2O3 nanoparticles (NPs). The cytotoxicity profile demonstrates the biocompatibility and negligible toxicity of the as-synthesized nanoprobes. The suggested approach provides a new class of gadolinium-based precursors which allows facile synthesis of highly crystalline Gd2O3 NPs