Ultrastable Matryoshka [Hf13] Nanocluster as a Luminescence Sensor for Concentrated Alkali and Acid.

作者：Xiao‐Min Kang, Han-Shi Hu, Zhi-Lei Wu, Jia‐Qi Wang, P. Cheng, Jun Li, Bin Zhao · 发表于：Angewandte Chemie · 年份：2019 · DOI：10.1002/anie.201907557 · 被引用次数：41 · 研究领域：Materials Science、Medicine

Stable metal clusters that can resist both highly concentrated acid and alkali are unknown. Herein, we present the first discrete neutral cluster, Hf13(μ4-O)8(OCH3)36 (1), which features extraordinary chemical stability with preserving crystalline state in both concentrated acid (10 M HNO3) and alkali (20 M boiling NaOH) aqueous solution. Importantly, 1 is the first luminescence probe for detecting both concentrated alkali (20 M NaOH) and strong acid (1 M HNO3) with high selectivity and repeatability. Theoretical studies of the electronic structure and bonding with density functional theory reveal that 1 has an extremely large HOMO-LUMO gap due to strong (d-p)π bonding that accounts for the ultrahigh stability. This work enriches functionalized metal clusters and luminescence sensor portfolio, laying the foundation for further construction of stable cluster-based materials.