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An Ultrastable Matryoshka [Hf 13 ] Nanocluster as a Luminescent Sensor for Concentrated Alkali and Acid
Author(s) -
Kang XiaoMin,
Hu HanShi,
Wu ZhiLei,
Wang JiaQi,
Cheng Peng,
Li Jun,
Zhao Bin
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201907557
Subject(s) - alkali metal , luminescence , aqueous solution , chemistry , cluster (spacecraft) , inorganic chemistry , chemical stability , materials science , organic chemistry , optoelectronics , computer science , programming language
Stable metal clusters that can resist both highly concentrated acid and alkali are unknown. Herein, we present a discrete neutral cluster, Hf 13 (μ 4 ‐O) 8 (OCH 3 ) 36 ( 1 ), which features extraordinary chemical stability by preserving its crystalline state in concentrated aqueous solutions of both acid (10 m HNO 3 ) and alkali (20 m boiling NaOH). Importantly, 1 can serve as a luminescent probe for detecting both concentrated alkali (20 m NaOH) and strong acid (1 m HNO 3 ) with high selectivity and repeatability. DFT studies of the electronic structure and bonding revealed that 1 has an extremely large HOMO–LUMO gap due to strong d π–p π bonding that accounts for the ultrahigh stability.