A Photoresponsive Receptor with a 105 Magnitude of Reversible Anion-Binding Switching

Einkauf, Jeffrey; Bryantsev, Vyacheslav; Moyer, Bruce A.; Custelcean, Radu

doi:10.1002/chem.202200719

A Photoresponsive Receptor with a 10⁵ Magnitude of Reversible Anion-Binding Switching

Journal Article · Wed Mar 23 00:00:00 EDT 2022 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202200719· OSTI ID:1862148

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

In a leap toward anion separation that uses only energy input for binding and release cycles, we report herein a new class of photoswitchable anion receptors featuring a diiminoguanidinium functionality that displays a change of more than five orders of magnitude in switched-off binding strength towards sulfate, a representative oxyanion, upon photoirradiation with UV light. Additionally, the (E,E)-2-pyridyl-diiminoguanidinium cation, synthesized as the triflate salt, binds sulfate with extraordinary strength in [D6]DMSO owing to its bidentate guanidinium hydrogen bonding, which can chelate the O-S-O edge of sulfate. Upon photoisomerization to the Z,Z isomer, the anion-binding site is essentially shut off by intramolecular hydrogen bonds to the 2-pyridyl substituents, as shown by anion-binding titrations, theoretical calculations, and X-ray structural analysis. This approach will allow the development of advanced anion-separation cycles that use only energy input and generate no chemical waste, and thus address challenging chemical separation problems in a more sustainable way.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1862148

Alternate ID(s):: OSTI ID: 1861143

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 26 Vol. 28; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2092856: Experimental Crystal Structure Determination D., Einkauf, Jeffrey; S., Bryantsev, Vyacheslav; A., Moyer, Bruce https://doi.org/10.5517/ccdc.csd.cc287sht The current record is supplemented by this dataset	dataset	January 2022
CCDC 2092857: Experimental Crystal Structure Determination D., Einkauf, Jeffrey; S., Bryantsev, Vyacheslav; A., Moyer, Bruce https://doi.org/10.5517/ccdc.csd.cc287sjv The current record is supplemented by this dataset	dataset	January 2022

A Photoresponsive Receptor with a 105 Magnitude of Reversible Anion-Binding Switching

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A Photoresponsive Receptor with a 10⁵ Magnitude of Reversible Anion-Binding Switching