Regulating Open Metal Sites in Metal-Organic Frameworks to Tame Luminescence Sensing
(2025) CCS Chemistry — Vol. 7, n° 5, p. 1396-1402 (2025)
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- Abstract
- Open metal sites (OMSs) represent a distinctive feature of metal-organic frameworks (MOFs), intertwined with guest accommodation and energy transfer within nanosized pores. Fine-tuning OMSs provide an effective approach to regulating MOF’s responsiveness and binding affinity towards guests, allowing for the construction of luminescent sensors for specific analytes. Such a strategy remains unexplored due to the inherent complexity of the systems and sensing mechanisms. Herein, we delicately regulated the OMSs in PCN-700 through multiple synthetic methodologies, including direct synthesis, linker installation, and linker exchange. The resultant MOFs consist of Zr6-clusters featuring various coordination numbers. Notably, PCN-700-8u with unsaturated 8-coordinated Zr-clusters exhibited the highest sensitivity in detecting a toxic pesticide pentachloronitrobenzene (PCNB) due to the presence of strong coordination interaction, as validated through single crystal X-ray diffraction directly. PCN-700-10u/12u bearing unsaturated 10/12-coordinated clusters perform lower quenching efficiencies than PCN-700-8u, but higher than PCN-700-12s with saturated clusters. In contrast, all these MOFs exhibit similar quenching efficiencies towards hexachlorobenzene for the absence of coordination interaction. This study not only develops a cost-effective and easily attainable material for PCNB detection, but also illuminates the pivotal importance of OMSs in customizing MOF-based sensors for practical applications.
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Citations
Han, Z., Guo, Y., Liang, R., Wang, K.-Y., Yang, Y., Mao, Y., Sun, T., Wang, M., Garcia, Y., Taylor, P. R., Shi, W., & Zhou, H.-C. (2025). Regulating Open Metal Sites in Metal-Organic Frameworks to Tame Luminescence Sensing. CCS Chemistry, 7(5), 1396-1402. https://doi.org/10.31635/ccschem.025.202404795 (Original work published 2025)