Supracluster assembly of an Al4 precursor toward the study of enhanced optical properties

Abstract

Supracluster assembly offers a unique opportunity for the isolation of customized materials using functional cluster precursors. Herein, for the first time, we demonstrate supracluster assembly based on an Al₄⁴⁻ precursor through both non-covalent interactions and coordination bonds. By reacting readily available, ultrastable, and soluble Al₄⁴⁻ as an anionic precursor with a metal center and neutral chelated chromophores, we successfully synthesized an extensive library of supracluster assembled crystalline solids, ranging from ion-pair structures, surface-modified clusters, and chains, to layered compounds. The advantage of this method is that it achieves stepwise performance regulation and enhancement using given functional precursors. These materials from supracluster assembly possess a broad range of tunable photophysical properties, including photoluminescence and third-order nonlinear optical (NLO) properties. Such extraordinary supracluster assembly will be widely applicable for creating a new generation of rationally organized solid materials with tailorable and customized properties.