Reversible dehalogenation in on-surface aryl-aryl coupling


JSON Export

{
  "id": "760", 
  "metadata": {
    "title": "Reversible dehalogenation in on-surface aryl-aryl coupling", 
    "doi": "10.24435/materialscloud:71-t1", 
    "license": "Creative Commons Attribution 4.0 International", 
    "keywords": [
      "SNSF", 
      "H2020", 
      "ONR", 
      "aryl-aryl coupling", 
      "dehalogenation", 
      "surface chemistry", 
      "Experimental"
    ], 
    "contributors": [
      {
        "affiliations": [
          "Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 D\u00fcbendorf, Switzerland", 
          "Institute of Physics, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne, Laboratory of Nanostructures at Surfaces, 1015 Lausanne, Switzerland"
        ], 
        "familyname": "Stolz", 
        "email": "samuel.stolz@empa.ch", 
        "givennames": "Samuel"
      }, 
      {
        "affiliations": [
          "Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 D\u00fcbendorf, Switzerland"
        ], 
        "familyname": "Di Giovannantonio", 
        "givennames": "Marco"
      }, 
      {
        "affiliations": [
          "Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 D\u00fcbendorf, Switzerland"
        ], 
        "familyname": "Urgel", 
        "givennames": "Jos\u00e9 I."
      }, 
      {
        "affiliations": [
          "Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 D\u00fcbendorf, Switzerland"
        ], 
        "familyname": "Sun", 
        "givennames": "Qiang"
      }, 
      {
        "affiliations": [
          "Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 D\u00fcbendorf, Switzerland"
        ], 
        "familyname": "Kinikar", 
        "givennames": "Amogh"
      }, 
      {
        "affiliations": [
          "Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 D\u00fcbendorf, Switzerland"
        ], 
        "familyname": "Borin Barin", 
        "givennames": "Gabriela"
      }, 
      {
        "affiliations": [
          "Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 D\u00fcbendorf, Switzerland"
        ], 
        "familyname": "Bommert", 
        "givennames": "Max"
      }, 
      {
        "affiliations": [
          "Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 D\u00fcbendorf, Switzerland", 
          "Department of Chemistry and Biochemistry, University of Bern, 3012 Bern, Switzerland"
        ], 
        "familyname": "Fasel", 
        "givennames": "Roman"
      }, 
      {
        "affiliations": [
          "Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 D\u00fcbendorf, Switzerland"
        ], 
        "familyname": "Widmer", 
        "email": "roland.widmer@empa.ch", 
        "givennames": "Roland"
      }
    ], 
    "_files": [
      {
        "description": "ReadMe File in yaml format listing the files contained in the record", 
        "checksum": "md5:eb5859f4da12efe10f592b4d5c472576", 
        "size": 58034, 
        "key": "ReadMe.yaml"
      }, 
      {
        "description": "zipped archive file containing all files of the record", 
        "checksum": "md5:38f3a1e2c634fc41d47d4df57ae20004", 
        "size": 39943743, 
        "key": "data.tgz"
      }
    ], 
    "references": [
      {
        "type": "Journal reference", 
        "doi": "10.1002/anie.202005443", 
        "citation": "S. Stolz, M. Di Giovannantonio, J.I. Urgel, Q. Sun, A. Kinikar, G. Borin Barin, M. Bommert, R. Fasel, R. Widmer, Angew. Chem. Int. Ed. 59, 14106 - 14110 (2020).", 
        "url": ""
      }
    ], 
    "conceptrecid": "759", 
    "version": 1, 
    "edited_by": 100, 
    "id": "760", 
    "owner": 243, 
    "mcid": "2021.37", 
    "is_last": true, 
    "status": "published", 
    "description": "The record contains the data to support the findings of our recent work on reversibility of the dehalogenation process in on-surface aryl-aryl coupling.\nIn the emerging field of on\u2010surface synthesis, dehalogenative aryl\u2013aryl coupling is unarguably the most prominent tool for the fabrication of covalently bonded carbon\u2010based nanomaterials. Despite its importance, the reaction kinetics are still poorly understood. Here we present a comprehensive temperature\u2010programmed x\u2010ray photoelectron spectroscopy investigation of reaction kinetics and energetics in the prototypical on\u2010surface dehalogenative polymerization of 4,4\u2032\u2032\u2010dibromo\u2010p\u2010terphenyl into poly(para\u2010phenylene) on two coinage metal surfaces, Cu(111) and Au(111). We find clear evidence for reversible dehalogenation on Au(111), which is inhibited on Cu(111) owing to the formation of organometallic intermediates. The incorporation of reversible dehalogenation in the reaction rate equations leads to excellent agreement with experimental data and allows extracting the relevant energy barriers. Our findings deepen the mechanistic understanding and call for its reassessment for surface\u2010confined aryl\u2013aryl coupling on the most frequently used metal substrates.", 
    "license_addendum": null, 
    "_oai": {
      "id": "oai:materialscloud.org:760"
    }, 
    "publication_date": "Mar 02, 2021, 14:33:44"
  }, 
  "revision": 6, 
  "updated": "2021-03-02T13:33:44.409000+00:00", 
  "created": "2021-03-02T10:14:19.695245+00:00"
}