Tuning the Lifetimes of Photoinduced Deligation in a Metal–Organic Framework via Linker Functionalization

Journal Article · Tue Sep 09 00:00:00 UTC 2025 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.5c09921 · OSTI ID:2998297

Ye, Qingyu  ^[1]; Herlinger, Isabelle A.  ^[2]; Fredin, Lisa A.  ^[2]; Cairnie, Daniel R. ^[1]; Yang, Xiaozhou  ^[1]; Yan, Minliang ^[1]; Morris, Amanda J.  ^[1]

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1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
2. Lehigh Univ., Bethlehem, PA (United States)

Recently photoinduced dynamic ligation in a metal–organic frameworks (MOFs) was reported, where a long-lived charge-transfer excited state (ca. 30 μs) featuring partial dissociation between the carboxylate linker and metal-based node was probed by time-resolved infrared (TRIR) spectroscopy. The study offers a new mechanistic perspective to evaluate the potential contribution from the excited state molecular configuration to the performance of MOF photocatalysts. In this work, by employing MIL-101(Fe) as the study platform, we have further explored the influence of intramolecular interactions on the stability of relevant excited states and demonstrated the effective tuning of their lifetimes through the incorporation of different functional groups into the system. The correlations between the varied excited state lifetimes and coordination configurations with specific functional groups (−NH₂ or −NO₂) was inferred from the analyses of infrared spectroscopic data and theoretical calculations, revealing the essential role of the intramolecular interactions (i.e., between the added functional groups and the carboxylate group) in the modulation of system energetics. Overall, the work presents a pathway to tune the excited state dynamics and expands the knowledge regarding the photoinduced dynamic ligation in carboxylate-based MOFs.

• Research Organization: American Chemical Society (ACS-C); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: SC0012445; SC0012446
• OSTI ID: 2998297
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 38 Vol. 147; ISSN 0002-7863; ISSN 1520-5126
• Publisher: American Chemical Society (ACS)Copyright Statement
• Country of Publication: United States
• Language: English