An Ultrastable Matryoshka [Hf13] Nanocluster as a Luminescent Sensor for Concentrated Alkali and Acid

Stable metal clusters that can resist both highly concentrated acid and alkali are unknown. Herein, we present a discrete neutral cluster, Hf₁₃(μ₄‐O)₈(OCH₃)₃₆ ( 1 ), which features extraordinary chemical stability by preserving its crystalline state in concentrated aqueous solutions of both acid (10 m HNO₃) 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 HNO₃) 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.