Icosahedron [Cl12]12- Templated Gigantic Gd158Co38 Nanocluster with the Largest Ln158 Core for Magnetic Cooling

Abstract

The synthesis of large nano-sized cluster-molecules is a goal that synthesists and structural scientists have been pursuing, as well as a huge challenge. Herein, the largest 3d-4f metal clusters Cl12@Gd158Co38 and Br12@Gd158Co38 until now are obtained through the “multi-anions-template” strategy, with a protein-sized metal frame (ca. 4.3 × 3.6 × 3.5 nm3). Different from the mixed distribution of 3d and 4f metals and the hollow structure in the previous giant 3d-4f clusters, for the dense core-shell structure Cl12@Gd158Co38 and Br12@Gd158Co38, the Ln158 core with the highest Ln nuclearity number is induced by icosahedra-shaped templates [Cl12]12- or [Br12]12-, while 3d metals (Co) are distributed on its periphery. Their appearances point out a new structure type of non-open giant Ln-based clusters (metal number > 100) and provide an ideal model for studying the multi-level assembly of complex macromolecules. Additionally, Cl12@Gd158Co38 shows the largest magnetic entropy change (-∆Smmax = 46.95 J kg-1 K-1 under 2.0 K and ΔH = 7 T) among reported high-nuclearity 3d-4f clusters.