Meltable Aluminum Molecular Rings with Fluorescence and Nonlinear Optical Properties

• Published in: Angewandte Chemie International Edition Vol. 63; no. 11; pp. e202400161 - n/a
• Main Authors: Wang, San‐Tai, Fang, Wei‐Hui, Zhang, Jian
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 11.03.2024
• Edition: International ed. in English
• Subjects: Aluminum; aluminum oxo cluster; Bonding strength; Clusters; crystal-liquid-glass; deep eutectic solvents; Hydrogen bonding; meltable; Melting point; Melting points; Nonlinear optics; optical limiting; Optical properties; Solvents; crystal-liquid-glass; meltable; optical limiting; aluminum oxo cluster; deep eutectic solvents
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202400161

Crystal–liquid–glass, which combines the tunable properties of crystalline compounds with the processability of glasses, has emerged as a new class of materials for fabricating bulk‐shapable devices in real applications. Inspired by the characteristics of deep eutectic solvent (DES) mixtures involving significant depressions in melting points compared to their neat constituent components, in this study, we designed and synthesized the first examples of meltable aluminum oxo clusters (AlOCs) via lattice doping with DESs at the molecular level. The abundant and strong hydrogen bonding between the aluminum molecular ring, DES components, and lattice solvents is postulated to be the root that affords melting point depressions and, thus, “melting” clusters. We prepared a transparent bubble‐free glass film under autogenous pressure using a hot‐press method. These cluster‐based films exhibited luminescent and nonlinear optical properties similar to those of pristine crystalline compounds. Our study belongs to the interdisciplinary disciplines of chemistry and physics. It not only breaks the limitations of crystalline glass on metal and ligand types but also acts as a general guide for extending the range of meltable crystalline materials. A comprehensive study of meltable aluminum molecular rings with precise lattice doping of deep eutectic solvents (DESs) shows that the abundant, complex and strong hydrogen bonds between the clusters and the DESs components is responsible for the melting behavior. The hot‐press method is used to prepare transparent bubble‐free cluster‐based glass films under autogenous pressure and study their fluorescence and nonlinear optical properties.