Anion-Guided Stepwise Assembly of High-Nuclearity Lanthanide Hydroxide Clusters

Angew Chem Int Ed Engl. 2022 Aug 15;61(33):e202205385. doi: 10.1002/anie.202205385. Epub 2022 May 19.

Abstract

The ability to construct complex molecular architectures with precise control is critical for realizing molecule-based materials and functions. Using the assembly of a 60-metal complex of ErIII with histidine as an example, we demonstrate the rational assembly of otherwise synthetically elusive polynuclear lanthanide hydroxide clusters directed by the combined set of I- and CO3 2- as templates. We succeeded in the stepwise transformation starting from Er12 to Er60 by way of two key intermediates Er34 and Er48 . The Er12 , Er34 , and Er48 core motifs represent respectively 1/6, 1/2, and 3/4 of the complete sodalite cage of Er60 . This work, representing a rare example of rationally constructing high-nuclearity lanthanide clusters guided by judiciously chosen templates, is expected to stimulate more future efforts for the controllable synthesis of complex molecular or supramolecular architectures with unprecedented structural sophistication and possibly useful properties.

Keywords: Anion Template; Clusters; Lanthanides; Polynuclear; Self-Assembly.