Leveraging Microenvironment Effects to Enhance Bifunctional Metal–Organic Framework-Catalyzed Aldol Reactions
- 1Department of Chemistry
- 2University of Washington
Abstract
Solvent effects are known to shift the position of chemical equilibria, alter reaction rates, and dictate the outcome of chemical transformations. Here, we show that tuning the pore surface chemistry of metal–organic framework (MOF) catalysts can mimic desirable solvent effects, more than doubling catalytic activity. First, we demonstrate that templated MOFs featuring bifunctional secondary amine–carboxylic acid pairs are effective catalysts for aldol reactions but exhibit high sensitivity to solvent polarity. Catalytic activity decreases dramatically upon increasing solvent polarity, likely due to the stabilization of off-cycle charged iminium intermediates. We show that high activity can be partially recovered by incorporating nonpolar n-hexyl chains into the framework backbone that destabilize charged species. Overall, this work highlights how precise control over the local pore environment can be a powerful tool for improving catalyst performance.
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BibTeX
@misc{rollins2026leveraging,
title = {{Leveraging Microenvironment Effects to Enhance Bifunctional Metal–Organic Framework-Catalyzed Aldol Reactions}},
author = {Devin S. Rollins and Kamaya Ronning and Amy E. Nam and Fubin Song and Phuong H. Le and Dianne J. Xiao},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010347/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010347/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Leveraging Microenvironment Effects to Enhance Bifunctional Metal–Organic Framework-Catalyzed Aldol Reactions
AU - Devin S. Rollins
AU - Kamaya Ronning
AU - Amy E. Nam
AU - Fubin Song
AU - Phuong H. Le
AU - Dianne J. Xiao
PY - 2026
DA - 2026/10/13
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010347/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010347/v1
AB - Solvent effects are known to shift the position of chemical equilibria, alter reaction rates, and dictate the outcome of chemical transformations. Here, we show that tuning the pore surface chemistry of metal–organic framework (MOF) catalysts can mimic desirable solvent effects, more than doubling catalytic activity. First, we demonstrate that templated MOFs featuring bifunctional secondary amine–carboxylic acid pairs are effective catalysts for aldol reactions but exhibit high sensitivity to solvent polarity. Catalytic activity decreases dramatically upon increasing solvent polarity, likely due to the stabilization of off-cycle charged iminium intermediates. We show that high activity can be partially recovered by incorporating nonpolar n-hexyl chains into the framework backbone that destabilize charged species. Overall, this work highlights how precise control over the local pore environment can be a powerful tool for improving catalyst performance.
ER -