Prof. Dr. Jean PINSON

Diazonium Salts and Analytical Chemistry

ITODYS UMR CNRS 7086 Sorbonne Paris Cite, Universite Paris Diderot 15, Rue Jean Antoine de Bai’f, 75013 PARIS Tel. : 33 1 57 27 72 21; e-mail: jean.pinson@univ-paris-diderot.fr
DIPLOMAS
1963: Chemical Engineer : Ecole Nationale Superieure des Industries Chimiques, Nancy.
1969: Doctor in Sciences, University of Paris.
Academic positions
1991-2000: Full Professor, University Paris 7.
2000 -2004: Chair Professor, University Paris 7.
2009- : Emeritus Professor, University Paris Diderot .
Industrial positions
1/09/85-28/02/86: Analysis department, Research center of Vitry, Rhone Poulenc (now Sanofi).
Sept 2004-Dec 2009 : Senior Scientist Alchimer (Massy, Fr) (now Aveni).
University Paris Diderot had patented my results concerning the electrografting of diazonium salts, Alchimer had bought a license of the patent and hired me to help in the development of the process. Two sister companies have used this reaction; Alchimer (now Aveni) for microelectronics (seed layers, TSV in the copper interconnect) and Alchimedics (now a subsidiary of Sinomedical) for medicine (Drug Eluting Stents). I still work under contract with this company.
Research Activities
My research activities have encompassed:
-Molecular electrochemistry : reduction of nitrogen heterocycles, oxidation of phenols, SRN1 electrocatalyzed reactions.
-Surface Chemistry: electrografting of amines, diazonium salts, alkyl halides.
I have published 167 research papers, 8 patents, 13 book chapters or reviews, co-edited a book, 5 proceedings.
I gave 159 presentations in meetings including conferences and seminars According to Web of Science my papers have been cited ~10000 times (h = 53).
My recent research activities have focused on Surface Chemistry, both at the university and in industry.
The characteristics of a material depend at the same time on its structural properties and its surface properties; the best example is given by cars where the steel body shows structural properties that provide among other things the protection of passengers; but this steel body would rapidly rust without a complex surface treatment that provide the protection against corrosion and the very commercially important aesthetics.
I have worked on the modification of surfaces by electrografting organic groups. I first discovered the grafting of amines by oxidation and then that of diazonium salts by reduction. These two reactions have been exploited by many colleagues for creating sensors, organic electronic devices, modified nanoobject such as graphene and nanotubes. In industry, the reduction of diazonium salts has been used by Alchimer for microelectronics, Alchimedics for medical devices, Cabot Corp for inks and paints and many start-ups are working on applications.
All these reactions are based on radical chemistry: the radicals react with the surface atoms to provide covalent surface-organic bonds. More recently we discovered that the aryl radicals obtained from diazonium salts can be prevented from reacting with surfaces by steric effect. As they cannot react with surfaces they abstract an atom (hydrogen, halogen) to give a second radical that reacts with surfaces. In this way it is possible to graft acetonitrile, iodo and bromoalkyl compounds, nitromethane on various surfaces metal, carbon, oxides, polymers.
Selected papers :
Nucleophile and aryl radical reactivity in SRN1 aromatic nucleophilic substitution reactions. Absolute and relative electrochemical determination. Christian Amatore, Mehmet A. Oturan, Jean Pinson, Jean Michel Saveant, Andre Thiebault J. Am. Chem. Soc., 1985, 107, 3451-3459.
Blandine Barbier, Jean Pinson, Georges Desarmot and Manuel Sanchez. Electrochemical Bonding of Amines to Carbon Fiber Surfaces Toward Improved Carbon-Epoxy Composites, J. Electrochem. Soc. 1990, 137, 1757-1764.
Mehmet A. Oturan, Jean Pinson. Hydroxylation by Electrochemically Generated OH° Radicals. Mono- and Polyhydroxylation of Benzoic Acid: Products and Isomer Distribution J. Phys. Chem., 1995, 99 (38), pp 13948-13954
Philippe Allongue, Michel Delamar, Bernard Desbat, Olivier Fagebaume, Rachid Hitmi, Jean Pinson, and Jean-Michel Saveant Covalent Modification of Carbon Surfaces by Aryl Radicals Generated from the Electrochemical Reduction of Diazonium Salts J. Am. Chem. Soc. 1997, 119, 201-207.
Jean Pinson and Fetah Podvorica Attachment of organic layers to conductive or semiconductive surfaces by reduction of diazonium salts. Chem. Soc. Rev., 2005, 34, 429-439. Electrografting, a powerful method for surface modification, Daniel Belanger, Jean Pinson, Daniel Belanger, Jean Pinson, Chem. Soc. Rev., 2011, 40 (7), 3995 – 4048.
Electrografting of Alkyl Films at Low Driving Force by Diverting the Reactivity of Aryl Radicals Derived from Diazonium Salts. Dardan Hetemi, Frederic Kanoufi, Catherine Combellas, Jean Pinson, Fetah I. Podvorica Langmuir 2014, 30, 13907-13913.
Surface Modification of Polymers by Reaction of Alkyl Radicals. Dardan Hetemi, Jerome Medard, Frederic Kanoufi, Catherine Combellas, Jean Pinson, and Fetah I. Podvorica. Langmuir 2016, 32, 512-518, DOI: 10.1021/acs.langmuir.5b03669.
Some theoretical and experimental insights on the mechanistic routes leading to the spontaneous grafting of gold surfaces by diazonium salts. Avni Berisha, Catherine Combellas, Frederic Kanoufi, Philippe Decorse, Nihal Oturan, Jerome Medard, Mahamadou Seydou, Francis Morel, Jean Pinson, Langmuir 2017, 33, 6677-6690, doi : 10.1021/acs.langmuir. 7b01371.
Surface functionalisation of polymers . Dardan Hetemi, Jean Pinson . Chem. Soc. Rev., 2017, DOI: 10.1039/C7CS00150A