An Ultrastable Matryoshka [Hf<sub>13</sub>] Nanocluster as a Luminescent Sensor for Concentrated Alkali and Acid

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  • Xiao‐Min Kang
    College of Chemistry, Key Laboratory of Advanced Energy Material Chemistry Nankai University Tianjin 300071 China
  • Han‐Shi Hu
    Department of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education Tsinghua University Beijing 100084 China
  • Zhi‐Lei Wu
    College of Chemistry, Key Laboratory of Advanced Energy Material Chemistry Nankai University Tianjin 300071 China
  • Jia‐Qi Wang
    Department of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education Tsinghua University Beijing 100084 China
  • Peng Cheng
    College of Chemistry, Key Laboratory of Advanced Energy Material Chemistry Nankai University Tianjin 300071 China
  • Jun Li
    Department of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education Tsinghua University Beijing 100084 China
  • Bin Zhao
    College of Chemistry, Key Laboratory of Advanced Energy Material Chemistry Nankai University Tianjin 300071 China

Abstract

<jats:title>Abstract</jats:title><jats:p>Stable metal clusters that can resist both highly concentrated acid and alkali are unknown. Herein, we present a discrete neutral cluster, Hf<jats:sub>13</jats:sub>(μ<jats:sub>4</jats:sub>‐O)<jats:sub>8</jats:sub>(OCH<jats:sub>3</jats:sub>)<jats:sub>36</jats:sub> (<jats:bold>1</jats:bold>), which features extraordinary chemical stability by preserving its crystalline state in concentrated aqueous solutions of both acid (10 <jats:sc>m</jats:sc> HNO<jats:sub>3</jats:sub>) and alkali (20 <jats:sc>m</jats:sc> boiling NaOH). Importantly, <jats:bold>1</jats:bold> can serve as a luminescent probe for detecting both concentrated alkali (20 <jats:sc>m</jats:sc> NaOH) and strong acid (1 <jats:sc>m</jats:sc> HNO<jats:sub>3</jats:sub>) with high selectivity and repeatability. DFT studies of the electronic structure and bonding revealed that <jats:bold>1</jats:bold> has an extremely large HOMO–LUMO gap due to strong d π–p π bonding that accounts for the ultrahigh stability.</jats:p>

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