How robust is the reversible steric shielding strategy for photoswitchable organocatalysts?


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{
  "metadata": {
    "is_last": true, 
    "publication_date": "Feb 24, 2022, 11:15:01", 
    "edited_by": 576, 
    "version": 1, 
    "license": "Creative Commons Attribution 4.0 International", 
    "license_addendum": null, 
    "_files": [
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        "key": "README.txt", 
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        "description": "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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    ], 
    "mcid": "2022.33", 
    "keywords": [
      "ERC", 
      "SNSF", 
      "EPFL", 
      "Photoswitchable organocatalysis", 
      "Statistical sampling", 
      "Reversible steric shielding"
    ], 
    "contributors": [
      {
        "givennames": "Simone", 
        "familyname": "Gallarati", 
        "affiliations": [
          "Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), 1015 Lausanne, Switzerland"
        ]
      }, 
      {
        "givennames": "Raimon", 
        "familyname": "Fabregat", 
        "affiliations": [
          "Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), 1015 Lausanne, Switzerland"
        ]
      }, 
      {
        "givennames": "Veronika", 
        "familyname": "Juraskova", 
        "affiliations": [
          "Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), 1015 Lausanne, Switzerland"
        ]
      }, 
      {
        "givennames": "Theo", 
        "familyname": "Jaffrelot Inizan", 
        "affiliations": [
          "Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), 1015 Lausanne, Switzerland"
        ]
      }, 
      {
        "givennames": "Clemence", 
        "email": "clemence.corminboeuf@epfl.ch", 
        "familyname": "Corminboeuf", 
        "affiliations": [
          "Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), 1015 Lausanne, Switzerland", 
          "National Center for Competence in Research \u2013 Catalysis (NCCR-Catalysis), \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), 1015 Lausanne, Switzerland", 
          "National Center for Computational Design and Discovery of Novel Materials (MARVEL), \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), 1015 Lausanne, Switzerland"
        ]
      }
    ], 
    "status": "published", 
    "doi": "10.24435/materialscloud:jw-sh", 
    "title": "How robust is the reversible steric shielding strategy for photoswitchable organocatalysts?", 
    "id": "1267", 
    "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\u2019 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 Br\u00f8nsted basicity of piperidine photoswitchable organocatalysts.", 
    "owner": 694, 
    "_oai": {
      "id": "oai:materialscloud.org:1267"
    }, 
    "conceptrecid": "1266", 
    "references": [
      {
        "citation": "S. Gallarati, R. Fabregat, V. Juraskova, T. Jaffrelot Inizan, C. Corminboeuf, J. Org. Chem. (2022), Under revision", 
        "type": "Journal reference"
      }
    ]
  }, 
  "updated": "2022-02-24T10:15:01.661895+00:00", 
  "revision": 2, 
  "id": "1267", 
  "created": "2022-02-24T09:57:50.248278+00:00"
}