On-surface coupling reactions on calcium carbonate

Abstract : Covalent coupling on metallic surfaces in UHV (Ultra High Vacuum) conditions is a new method for preparing molecular structures otherwise impossible to achieve in solution (graphene nanoribbons, 2D polymers for instance). The major challenge is now to extend these reactions from metallic to insulating surfaces, for future applications as, for instance, in molecular electronics. In particular, the coupling reaction of benzoic acid derivatives, grafted on calcite via carboxylic groups, has been demonstrated for the first time in UHV conditions. In the first part of this work, we synthesized precursor molecules for specific reactions (homocoupling of ethynes, photopolymerization, polycondensation and Ullmann reaction) on calcium carbonate in UHV conditions. In the second part of this work we extended this investigation up to the macroscale level (semi-preparative) by grafting molecules on calcium carbonate microparticles, followed by reaction activation and finally by dissolution of the substrate in order to recover the coupling products. The calcium carbonate microparticles were prepared by grinding commercial product or by spray pyrolysis and were fully characterized by FTIR, TG/DTG, XRD, SEM and BET techniques. Then, after grafting of organic reactant, the reactions were activated with two different solvent-free methods: by grinding in a planetary milling machine or by heating the samples in a furnace under vacuum. Whereas in UHV conditions, 4-iodobenzoic acid affords biphenyldicarboxylic acid, mechanochemical condition gives benzoic acid and thermal activation the dibenzoic acid ether.
Document type :
Theses
Complete list of metadatas

Cited literature [160 references]  Display  Hide  Download

https://tel.archives-ouvertes.fr/tel-01356668
Contributor : Abes Star <>
Submitted on : Friday, August 26, 2016 - 10:09:10 AM
Last modification on : Monday, April 29, 2019 - 3:31:13 PM
Long-term archiving on : Sunday, November 27, 2016 - 12:24:51 PM

File

2015TOU30158.pdf
Version validated by the jury (STAR)

Identifiers

  • HAL Id : tel-01356668, version 1

Citation

Chiara Venturini. On-surface coupling reactions on calcium carbonate. Other. Université Paul Sabatier - Toulouse III, 2015. English. ⟨NNT : 2015TOU30158⟩. ⟨tel-01356668⟩

Share

Metrics

Record views

251

Files downloads

770