2016
DOI: 10.1021/jacs.6b05626
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A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal–Organic Framework

Abstract: We describe a new strategy to generate non-coordinating anions using zwitterionic metal-organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO2)4](-)) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of Mn(III)- and Fe(III)-porphyrins in the zwitteri… Show more

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Cited by 85 publications
(49 citation statements)
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“…Notably, compared with Brønsted-or Lewis-acid catalysts, the coordination mode and/or spin state of earth-abundant transition metal (e.g., iron) catalysts can be tuned by using different ligands with different electronic and steric effects, which could alter the reaction mechanism as well as reaction dynamics of other reactions. Our proposed metal effects could also be relevant to other metal-catalyzed cycloaddition reactions, and may help the design of homogeneous, heterogeneous 11,65 , and artificial biological catalysts 6,69,70 for this synthetically challenging ODA reaction.…”
Section: Discussionmentioning
confidence: 96%
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“…Notably, compared with Brønsted-or Lewis-acid catalysts, the coordination mode and/or spin state of earth-abundant transition metal (e.g., iron) catalysts can be tuned by using different ligands with different electronic and steric effects, which could alter the reaction mechanism as well as reaction dynamics of other reactions. Our proposed metal effects could also be relevant to other metal-catalyzed cycloaddition reactions, and may help the design of homogeneous, heterogeneous 11,65 , and artificial biological catalysts 6,69,70 for this synthetically challenging ODA reaction.…”
Section: Discussionmentioning
confidence: 96%
“…Also, dispersion interactions and an oriented external electric field (OEEF) can facilitate the ODA reaction. Therefore, an OEEF may be applied to heterogeneous-type (e.g., MOF 11 and single-atom catalysis 65 ) catalysis and artificial metalloenzymes 6,66-70 for the ODA reaction. Moreover, steric and electronic effects were computationally shown to be the key factors responsible for the uncommon C=O chemoselectivity, and this was experimentally verified.…”
Section: Discussionmentioning
confidence: 99%
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“…The COF environment could furnish a catalytic cobalt center with a more delocalized electronic structure, thus facilitating the electrocatalytic CO 2 reduction. In another recent important work, Johnson et al constructed zwitteronic MOFs by assembling anionic secondary building blocks ([In(CO 2 ) 4 ] − ) with cationic metalloporphyrin‐based organic through solvothermal reactions . The change of coordination environment in the porphyrin metal center resulted from anion metathesis was analyzed by using single‐crystal X‐ray diffraction, UV–vis spectra, and X‐ray photoelectron spectroscopy (XPS ) spectra.…”
Section: Rational Design Of the Diverse Catalytic Sites In Crystallinmentioning
confidence: 99%
“…c) Zwitterionic MOF structure and its catalytic applications for three representative organic transformations. Reproduced with permission . Copyright 2016, American Chemical Society.…”
Section: Rational Design Of the Diverse Catalytic Sites In Crystallinmentioning
confidence: 99%