Direct Observation of Modulated Radical Spin States in Metal–Organic Frameworks by Controlled Flexibility

Chen, Xiaofeng; Xie, Haomiao; Lorenzo, Emmaline R.; Zeman, Charles J.; Qi, Yue; Syed, Zoha H.; Stone, Aaron E. B. S.; Wang, Yao; Goswami, Subhadip; Li, Peng; Islamoglu, Timur; Weiss, Emily A.; Hupp, Joseph T.; Schatz, George C.; Wasielewski, Michael R.; Farha, Omar K.

doi:10.1021/jacs.1c11417

Title: Direct Observation of Modulated Radical Spin States in Metal–Organic Frameworks by Controlled Flexibility

Journal Article · 06 February 2022 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.1c11417 · OSTI ID:2001249

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^[2]; Qi, Yue ^[2];

^[2]; Stone, Aaron E. B. S. ^[2];

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Shanghai Normal University (China); Northwestern University, Evanston, IL (United States); Northwestern University
Northwestern University, Evanston, IL (United States)
Fudan University, Shanghai (China)

Owing to their switchable spin states and dynamic electronic character, organic-based radical species have been invoked in phenomena unique to a variety of fields. When incorporated in solid state materials, generation of organic radicals proves challenging due to aggregation. Metal–organic frameworks (MOFs) are promising candidates for immobilization and stabilization of organic radicals because of the tunable spatial arrangement of organic linkers and metal nodes, which sequesters the reactive species. Herein, a flexible, redox-active tetracarboxylic acid linker bearing two imidazole units was chosen to construct a new Zr₆-MOF, NU-910, with scu topology. By exploiting the structural flexibility of NU-910, we successfully modulate the dynamics between an isolated organic radical species and an organic radical π-dimer species in the MOF system. Single-crystal X-ray diffraction analysis reveals that through solvent exchange from N,N-diethylformamide to acetone, NU-910 undergoes a structural contraction with interlinker distances decreasing from 8.32 Å to 3.20 Å at 100 K. Organic radical species on the bridging linkers are generated via UV light irradiation. Direct observation of temperature-induced spin switches from an isolated radical species to a magnetically silent radical π-dimer in NU-910 after irradiation in the solid state was achieved via variable-temperature single-crystal X-ray diffraction and variable-temperature electron paramagnetic resonance spectroscopy. Ultraviolet–visible–near infrared spectroscopy and density functional theory calculations further substantiated the formation of a radical cation π-dimer upon irradiation. As a result, this work demonstrates the potential of using flexible MOFs as a platform to modulate radical spin states in the solid phase.

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Research Organization:: Northwestern University, Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021314; SC0012702

OSTI ID:: 2001249

Alternate ID(s):: OSTI ID: 1978452

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 6 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Direct Observation of Modulated Radical Spin States in Metal–Organic Frameworks by Controlled Flexibility

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