Simone Gallarati¹, Raimon Fabregat¹, Veronika Juraskova¹, Theo Jaffrelot Inizan¹, Clemence Corminboeuf^1,2,3*

1 Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

2 National Center for Competence in Research – Catalysis (NCCR-Catalysis), École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

3 National Center for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

* Corresponding authors emails: clemence.corminboeuf@epfl.ch

DOI10.24435/materialscloud:jw-sh [version v1]

Publication date: Feb 24, 2022

How to cite this record

Simone Gallarati, Raimon Fabregat, Veronika Juraskova, Theo Jaffrelot Inizan, Clemence Corminboeuf, How robust is the reversible steric shielding strategy for photoswitchable organocatalysts?, Materials Cloud Archive 2022.33 (2022), https://doi.org/10.24435/materialscloud:jw-sh

Description

A highly appealing strategy to modulate a catalyst's activity and/or selectivity in a dynamic and non-invasive way is to incorporate a photoresponsive unit into a catalytically competent molecule. However, the description of the photoinduced conformational or structural changes that alter the catalyst's intrinsic reactivity is often reduced to a handful of intuitive static representations, which can struggle to capture the complexity of flexible organocatalysts. Here, we show how a comprehensive exploration of the free energy landscape of N-alkylated azobenzene-tethered piperidine catalysts is essential to unravel the conformational characteristics of each configurational state and explain the experimentally observed reactivity trends. Mapping the catalysts’ conformational space highlights the existence of false ON or OFF states that lower their switching ability. Our findings expose the challenges associated with the realisation of reversible steric shielding for the photocontrol of Brønsted basicity of piperidine photoswitchable organocatalysts.

Materials Cloud sections using this data

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File name	Size	Description
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data.tar.gz MD5md5:27d05becabda33d82ddc26423ca2ac8b	63.9 MiB	File containing the relevant data to generate the plots and tables in the article, including molecular geometries and thermodynamic data. See the README file for more details.

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External references

Keywords

ERC SNSF EPFL Photoswitchable organocatalysis Statistical sampling Reversible steric shielding