In Situ Synthesis of Well‐Ordered Magnetic Palladium Catalyst Triggered by Supramolecular Chaotropic Effect of Boron Cluster

Abstract Supramolecular chaotropic effect is a new topic in the field of nanocomposites (NCs) fabrication. Herein, this strategy was applied to prepare magnetic Fe₃O₄@γ‐CD‐boron cluster (SSAs)@Pd NCs in situ via a facile two‐step process, involving a supramolecular assembly process on Fe₃O₄ NPs and in situ formation of Pd nanoparticles. Boron clusters ([closo‐B₁₂H₁₂]²⁻) played a dual role in this synthetic process, and were used as a superchaotropic anion to interact with γ‐CD to form supramolecular self‐assemblies (SSAs), as well as efficient reductant to in situ reduce Pd(II) to Pd(0). Ascribed to the electrostatic attraction of boron clusters and capping effect of γ‐CD, ultrafine Pd nanoparticles were successfully coated on the Fe₃O₄@SSAs composites to fabricate Fe₃O₄@SSAs@Pd NCs. A combination of UV spectra, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, transmission electron microscopy, X‐ray diffraction, and energy dispersive X‐ray spectroscopy was used to verify the formation of these magnetic Pd NCs. The ultrafine metallic Pd NPs imparted the magnetic composites with great potential in catalysis, especially for Suzuki coupling reactions. Remarkably, the obtained Fe₃O₄@SSAs@Pd NCs showed good catalytic performance, high stability and easy recycling via an external magnet.