Real‐Time In Situ Volatile Organic Compound Sensing by a Dual‐Emissive Polynuclear Ln‐MOF with Pronounced LnIII Luminescence Response

作者：Pang JingJing; Yao ZhaoQuan; Zhang Kuo; Li QuanWen; Fu ZiXuan; Zheng Ran; Li Wei; Xu Jian; Bu XianHe

来源：Angewandte Chemie, 2023, 135(7).

DOI：10.1002/ANGE.202217456

• Lanthanide Polynuclear Clusters
• Metal–Organic Frameworks
• Ratiometric Luminescence Behavior
• Temperature Sensing
• Volatile Organic Compound Detection

Lanthanide metal–organic frameworks (Ln‐MOFs) are promising for luminescence detection of volatile organic compound (VOC) vapors, but usually suffer from the silent or quenched Ln3+ emission. Herein, we report a new dual‐emissive Eu‐MOF composed of the coordinatively unsaturated Eu9 clusters that afford abundant open metal sites to form a confined “binding pocket” to facilitate the preconcentration and recognition of VOCs. Single‐crystal structural analyses reveal that specific analytes can replace the OH oscillators in the first coordination sphere of Eu3+ and form a unique hydrogen‐bonding second‐sphere adduct tying adjacent Eu9 clusters together to minimize their nonradiative vibrational decay. With the promoted Eu3+ luminescence, the MOF realizes real‐time in situ visual sensing of THF vapor (<1?s) and shows a quantitative ratiometric response to the vapor pressure with a limit of detection down to 17.33?Pa. Also, it represents a top‐performing ratiometric luminescent thermometer.(#br)A dual‐emissive polynuclear Eu‐MOF enriched with abundant potential open metal sites was constructed. In terms of a novel recognition‐transduction protocol, this material realized real‐time in situ visual detection of THF vapor (<1?s) while showing a quantitative ratiometric response to vapor pressure with an ultralow limit of detection.

• 单位
  南开大学; 元素有机化学国家重点实验室