Article
Stimuli-Modulated Metal Oxidation States in Photochromic MOFs
Journal of the American Chemical Society
(2022)
Abstract
Tuning metal oxidation states in metal–organic framework (MOF) nodes by switching between two discrete linker photoisomers via an external stimulus was probed for the first time. On the examples of three novel photochromic copper-based frameworks, we demonstrated the capability of switching between +2 and +1 oxidation states, on demand. In addition to crystallographic methods used for material characterization, the role of the photochromic moieties for tuning the oxidation state was probed via conductivity measurements, cyclic voltammetry, and electron paramagnetic resonance, X-ray photoelectron, and diffuse reflectance spectroscopies. We confirmed the reversible photoswitching activity including photoisomerization rate determination of spiropyran- and diarylethene-containing linkers in extended frameworks, resulting in changes in metal oxidation states as a function of alternating excitation wavelengths. To elucidate the switching process between two states, the photoisomerization quantum yield of photochromic MOFs was determined for the first time. Overall, the introduced noninvasive concept of metal oxidation state modulation on the examples of stimuli-responsive MOFs foreshadows a new pathway for alternation of material properties toward targeted applications.
Disciplines
Publication Date
February, 2022
DOI
10.1021/jacs.1c11984
Citation Information
Corey R. Martin, Kyoung C. Park, Gabrielle A. Leith, Jierui Yu, et al.. "Stimuli-Modulated Metal Oxidation States in Photochromic MOFs" Journal of the American Chemical Society Vol. 144 Iss. 10 (2022) p. 4457 - 4468 Available at: http://works.bepress.com/emily-barth/3/