Aryl Diazonium Salts E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 612

Veröffentlichungsjahr: 2012

Beschreibung

Diazonium compounds are employed as a new class of coupling agents to link polymers, biomacromolecules, and other species (e. g. metallic nanoparticles) to the surface of materials. The resulting high performance materials show improved chemical and physical properties and find widespread applications. The advantage of aryl diazonium salts compared to other surface modifiers lies in their ease of preparation, rapid (electro)reduction, large choice of reactive functional groups, and strong aryl-surface covalent bonding.

This unique book summarizes the current knowledge of the surface and interface chemistry of aryl diazonium salts. It covers fundamental aspects of diazonium chemistry together with theoretical calculations of surface-molecule bonding, analytical methods used for the characterization of aryl layers, as well as important applications in the field of electrochemistry, nanotechnology, biosensors, polymer coatings and materials science. Furthermore, information on other surface modifiers (amines, silanes, hydrazines, iodonium salts) is included. This collection of 14 self-contained chapters constitutes a valuable book for PhD students, academics and industrial researchers working on this hot topic.

Leseprobe

Table of Contents

Cover

Related Titles

Title page

Copyright page

Dedication

Preface

List of Contributors

1 Attachment of Organic Layers to Materials Surfaces by Reduction of Diazonium Salts

1.1 A Brief Survey of the Chemistry and Electrochemistry of Diazonium Salts

1.2 The Different Methods that Permit Grafting of Diazonium Salts

1.3 The Different Substrates, Diazonium Salts, and Solvents that Can Be Used

1.4 Evidence for the Presence of a Bond between the Substrate and the Organic Layer

1.5 From Monolayers to Multilayers

1.6 Structure and Formation of Multilayers

1.7 Conclusion

2 Aryl–Surface Bonding: A Density Functional Theory (DFT) Simulation Approach

2.1 Introduction

2.2 Density Functional Theory

2.3 Bonding between Aryl and Various Substrates

2.4 Summary and Outlook

Acknowledgments

3 Patterned Molecular Layers on Surfaces

3.1 Methods Based on Scanning Probe Lithography

3.2 Methods Based on Soft Lithography

3.3 Methods Based on Lithography

3.4 Methods Based on Surface-Directed Patterning

3.5 Summary and Conclusions

4 Analytical Methods for the Characterization of Aryl Layers

4.1 Introduction

4.2 Scanning Probe Microscopies

4.3 UV–VIS Spectroscopy: Transmission, Reflection, and Ellipsometry

4.4 IR Spectroscopy

4.5 Raman Spectroscopy and Surface-Enhanced Raman Scattering (SERS)

4.6 X-ray Photoelectron Spectroscopy (XPS)

4.7 X-ray Standing Waves (XSW)

4.8 Rutherford Backscattering

4.9 Time of Flight Secondary Ion Mass Spectroscopy

4.10 Electrochemistry

4.11 Contact Angle Measurements

4.12 Conclusion

5 Modification of Nano-objects by Aryl Diazonium Salts

5.1 Introduction

5.2 Electrochemical Modification of Nano-objects by Reduction of Diazonium Salts

5.3 Chemical Modification of Nano-objects by Reduction of Diazonium Salts

5.4 Summary and Conclusions

Acknowledgments

6 Polymer Grafting to Aryl Diazonium-Modified Materials: Methods and Applications

6.1 Introduction

6.2 Methods for Grafting Coupling Agents from Aryl Diazonium Compounds

6.3 Grafting Macromolecules to Surfaces through Aryl Layers

6.4 Adhesion of Polymers to Surfaces through Aryl Layers

6.5 Conclusion

7 Grafting Polymer Films onto Material Surfaces: The One-Step Redox Processes

7.1 Cathodic Electrografting (CE) in an Organic Medium

7.2 Surface Electroinitiated Emulsion Polymerization (SEEP)

7.3 Chemical Grafting via Chemical Redox Activation (Graftfast™)

7.4 Summary and Conclusions

8 Electrografting of Conductive Oligomers and Polymers

8.1 Introduction

8.2 Conjugated Oligomers and Polymers

8.3 Surface Grafting Based on Electroreduction of Diazonium Salts

8.4 Polyphenylene and Oligophenylene-Tethered Surface Prepared by the Diazonium Reduction of Aniline or 4-Substituted Aniline

8.5 n-Doping and Conductance Switching of Grafted Biphenyl, Terphenyl, Nitro-biphenyl and 4-Nitroazobenzene Mono- and Multilayers

8.6 p-Doping and Conductance Switching of Grafted Oligo-Phenylthiophene or Oligothiophene Mono- and Multilayers

8.7 p-Doping and Conductance Switching of Grafted Oligoaniline Mono- and Multilayers

8.8 Conclusion and Outlook

9 The Use of Aryl Diazonium Salts in the Fabrication of Biosensors and Chemical Sensors

9.1 Introduction

9.2 The Important Features of Aryl Diazonium Salts with Regard to Sensing

9.3 Sensors and Biosensors Fabricated Using Aryl Diazonium Salts

9.4 Conclusions

10 Diazonium Compounds in Molecular Electronics

10.1 Introduction

10.2 Fabrication of Molecular Junctions Using Diazonium Reagents

10.3 Electronic Performance of Diazonium-Derived Molecular Junctions

10.4 Summary and Outlook

Acknowledgments

11 Electronic Properties of Si Surfaces Modified by Aryl Diazonium Compounds

11.1 Introduction

11.2 Experimental Techniques to Characterize Electronic Properties of Si Surfaces in Solutions

11.3 Conclusion and Outlook

Acknowledgments

12 Non-Diazonium Organic and Organometallic Coupling Agents for Surface Modification

12.1 Amines

12.2 Arylhydrazines

12.3 Aryltriazenes

12.4 Alcohols

12.5 Grignard Reagents

12.6 Onium Salts

12.7 Alkyl Halides

12.8 Conclusion

13 Various Electrochemical Strategies for Grafting Electronic Functional Molecules to Silicon

13.1 Introduction

13.2 Architecture of Hybrid Devices

13.3 Electrografting of Monolayers to Si

13.4 Negative Differential Resistance Effect in a Monolayer Electrografted Using a Diazonium Complex

13.5 Dielectric Monolayers Electrografted Using Silanes

13.6 Molecular Diodes Based on C60/Porphyrin-Derivative Bilayers

13.7 Memory Effect in TPP-C11 Monolayers Electrografted Using a C=C Linker

13.8 Summary

14 Patents and Industrial Applications of Aryl Diazonium Salts and Other Coupling Agents

14.1 Introduction

14.2 Patents

14.3 Industrial Applications

14.4 Conclusion

Index

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Electrochemical Surface Modification

Thin Films, Functionalization and Characterization

Series: Advances in Electrochemical Sciences and Engineering (Volume 10)

Series edited by Alkire, R. C., Kolb, D. M., Lipkowski, J., and Ross, P.

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ISBN: 978-3-527-31419-5

The Editor

Dr. Mohamed Mehdi Chehimi

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

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The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.

© 2012 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

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Print ISBN: 978-3-527-32998-4

ePDF ISBN: 978-3-527-65047-7

ePub ISBN: 978-3-527-65046-0

mobi ISBN: 978-3-527-65045-3

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Cover Design Adam-Design, Weinheim

Typesetting Toppan Best-set Premedia Limited, Hong Kong

To Jean Pinson, with gratitude

Preface

Dear Reader,

The diazotation of compounds has first been described in the mid-19th century by the German chemist Peter Griess. Henceforth, aryl diazonium salts (from the French “diazote”, two nitrogen atoms) are commonly used for the synthesis of a large series of organic compounds such as azo dyes, and are thus the object of numerous articles and book chapters or sections. However, the study of the surface and interface chemistry of these salts remained sparse despite its interest in modifying materials surfaces. For example, it was shown in 1958 that the reaction of aryl diazonium salts with mercury electrodes results in electrografting of aryl groups on this liquid metal with formation of phenylmercuric chloride and diphenylmercury (Elofson, R.M., Can. J. Chem., 1958, 36, 1207–1210, doi: 10.1139/v58-174; see also Chapter 1). Later in 1961, aryl diazonium salts were proposed as coupling agents in histochemistry for the labeling of enzymes (Burstone, M.S., Weisburger, E.K., J. Histochem. Cytochem., 1961, 9, 301–303, doi: 10.1177/9.3.301).

In modern surface science, Jean Pinson and co-workers described, in 1992, the mechanisms of the reaction between aryl diazonium salts and glassy carbon electrodes resulting in surface-tethered aryl groups. Provided that the functional group, in para position of the diazonium, is reactive, it becomes possible to graft polymers, enzymes, catalysts, etc. Since then, the two last decades (1992–2012) witnessed a quantum jump in the number of publications pertaining to surface chemistry and applications of aryl diazonium salts. The interest in using these compounds obviously lies in their ease of preparation, rapid reduction by a large range of methods and strong aryl-surface covalent bonding. Grafted aryl groups can be used as such in order to impart new physicochemical properties, or can serve as coupling agents for additional species. The applications concern electronics, electrocatalysis, sensors, nanocomposites, drug delivery, to name but a few, as testified by over 3000 articles and reviews, book chapters, and chapter sections. Several processes involving aryl diazonium salts were also patented and industrial products, though not too many, are on the market (see Chapter 14). Despite these extraordinary academic and industrial achievements, there is no comprehensive book dealing with the fundamental aspects of surface and interface chemistry of the diazonium salts and their use as surface modifiers and coupling agents. The book that you are holding in your hands fills this gap in 14 self-contained chapters written by acknowledged experts in their respective fields.

One can distinguish three main parts: fundamental and analytical aspects of diazonium-modified surfaces (Chapters 1–4); applications of diazonium salts in electrocatalysis, polymer science, sensors and biosensors, and electronics (Chapters 5–11). The third part concerns related or alternative organic molecules (e.g. amines, triazenes, vinyl, ethynyl, Grignard reagents) for surface treatment in general (Chapter 12) and for the more applied molecule-silicon electronics, in particular (Chapter 13). The book finishes by a contribution summarizing patents and industrial applications of the surface chemistry of aryl diazonium salts and related compounds (Chapter 14).

Dear Reader, we would like to thank you for choosing our book. As you will appreciate, the surface chemistry of diazonium salts and related compounds has progressed at a remarkable pace. The gap between the academic research on diazonium salt surface chemistry and its industrial applications has already been filled although this topic of surface science and technology is still in its infancy. Whether you are a student, technician, engineer, teacher or researcher; expert or newcomer, it is hoped that the information provided by all contributors will open new horizons.

As an editor, it has been a very exciting experience to collaborate with acknowledged experts from the five continents. I should like to thank them all for kindly accepting my invitations to contribute to this adventure. I am also very much indebted to all reviewers for their guidance. I am grateful to my colleague, Dr. Abderrahim Boudenne (Université Paris Est Créteil, France), for his remarkable help when I started the book project. I must also add here that I, personally, as well as my students, have learned a lot from Professor Jean Pinson. I have enjoyed his teaching of chemical kinetics and magneto-chemistry when I was one of his third year students in 1981 at University Paris 7; it is both and an honor and a privilege to have him as a colleague 30 years later. It therefore gives me great pleasure to dedicate this book to my former professor of chemistry and actual colleague and friend Jean Pinson.

This experience has been intense and exciting over almost 2 years. It would not have been possible to put the book in its final form, in such a short period of time, without the continuous support, encouragement, love, and patience of my daughter Inès, my son Selim, and my wife Heger.

Mohamed Mehdi ChehimiMarch 2012

List of Contributors

Dinesh K. Aswal

Bhabha Atomic Research Centre

Technical Physics Division

Trombay

Mumbai 400 085

India

James A. Belmont

Cabot Corporation Business and Technology Center

157 Concord Road

P.O. Box 7001

Billerica

MA 01821

USA

Adam Johan Bergren

University of Alberta

National Institute for Nanotechnology

11421 Saskatchewan Drive

Edmonton

AB T6G 2M9

Canada

Christophe Bureau

Advanced Material Technology Consulting

9 Avenue Paul Verlaine

38030 Grenoble Cedex 2

France

Mohamed M. Chehimi

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

Sheng Dai

Oak Ridge National Laboratory

Chemical Sciences Division

P.O. Box 2008, MS 6201

Oak Ridge

TN 37831-6201

USA

and

University of Tennessee

Department of Chemistry

Knoxville

TN 37966

USA

Guy Deniau

CEA-Saclay

IRAMIS

SPCSI Chemistry of Surfaces and Interfaces Group

91191 Gif-sur-Yvette

France

Alison J. Downard

University of Canterbury

Department of Chemistry

MacDiarmid Institute for Advanced Materials and Nanotechnology

Private Bag 4800

Christchurch 8140

New Zealand

Sarra Gam-Derouich

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

Jalal Ghilane

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

J. Justin Gooding

University of New South Wales

School of Chemistry and Australian Centre for NanoMedicine

Sydney 2052

Australia

Andrew J. Gross

University of Canterbury

Department of Chemistry

MacDiarmid Institute for Advanced Materials and Nanotechnology

Private Bag 4800

Christchurch 8140

New Zealand

Alicia L. Gui

University of New South Wales

School of Chemistry

Sydney 2052

Australia

Dao-Jun Guo

Qufu Normal University

School of Chemistry and Chemical Engineering

The Key Laboratory of Life-Organic Analysis

Qufu

Shandong 273165

China

Shiv Kumar Gupta

Bhabha Atomic Research Centre

Technical Physics Division

Trombay

Mumbai 400 085

India

Karsten Hinrichs

Leibniz-Institut für Analytische Wissenschaften – ISAS- e.V.

Department Berlin

Albert-Einstein-Straße 9

12489 Berlin

Germany

De-en Jiang

Oak Ridge National Laboratory

Chemical Sciences Division

P.O. Box 2008, MS 6201

Oak Ridge

TN 37831-6201

USA

Shankar Prasad Koiry

Bhabha Atomic Research Centre

Technical Physics Division

Trombay

Mumbai 400 085

India

Jean Christophe Lacroix

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

Guozhen Liu

Central China Normal University

Key Laboratory of Pesticide and Chemical Biology of Ministry of Education

College of Chemistry

152# Luoyu Road

Wuhan 430079

China

Samia Mahouche-Chergui

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

Pascal Martin

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

Richard McCreery

University of Alberta

National Institute for Nanotechnology

11421 Saskatchewan Drive

Edmonton

AB T6G 2M9

Canada

Alice Mesnage

CEA-Saclay

IRAMIS

SPCSI Chemistry of Surfaces and Interfaces Group

91191 Gif-sur-Yvette

France

Fakhradin Mirkhalaf

Coventry University

Sonochemistry Centre

Coventry, CV1 5FB

UK

Nanomedpharma (NMP) Ltd

Eden Building

Liverpool Hope University

Hope Park

Liverpool, L16 9JD

UK

Serge Palacin

CEA-Saclay

IRAMIS

SPCSI Chemistry of Surfaces and Interfaces Group

91191 Gif-sur-Yvette

France

Jean Pinson

ESPCI, Laboratoire Sciences Analytiques, Bioanalytiques et Miniaturisation

10 rue Vauquelin

75231 Paris Cedex 05

France

and

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

Fetah I. Podvorica

University of Prishtina

Faculty of Mathematical and Natural Sciences

Chemistry Department

rr. “Nena Tereze” nr. 5

10 000 Prishtina

Kosovo

Hyacinthe Randriamahazaka

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

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Jörg Rappich

Helmholtz-Zentrum Berlin für Materialien und Energie GmbH

Institut für Silizium-Photovoltaik

Kekuléstraße 5

12489 Berlin

Germany

Hatem Ben Romdhane

Campus Universitaire

Faculté des Sciences de Tunis

Laboratoire de Chimie Organique Structurale et Macromoléculaire

2092 El Manar II

Tunisia

Katy Roodenko

The University of Texas at Dallas

Department of Materials Science & Engineering

Mail Station RL10

800 W. Campbell Road

Richardson

TX 75080-3021

USA

Luis Santos

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

Nan Shao

Oak Ridge National Laboratory

Chemical Sciences Division

P.O. Box 2008, MS 6201

Oak Ridge

TN 37831-6201

USA

Bradley M. Simons

University of Canterbury

Department of Chemistry

MacDiarmid Institute for Advanced Materials and Nanotechnology

Private Bag 4800

Christchurch 8140

New Zealand

Lorraine Tessier

CEA-Saclay

IRAMIS

SPCSI Chemistry of Surfaces and Interfaces Group

91191 Gif-sur-Yvette

France

Gaelle Trippe-Allard

University Paris Diderot

Sorbonne Paris Cité

ITODYS

UMR CNRS 7086

15 rue J-A de Baïf

75013 Paris

France

Xin Zhang

Helmholtz-Zentrum Berlin für Materialien und Energie GmbH

Institut für Silizium-Photovoltaik

Kekuléstraße 5

12489 Berlin

Germany

1

Attachment of Organic Layers to Materials Surfaces by Reduction of Diazonium Salts

Jean Pinson

1.1 A Brief Survey of the Chemistry and Electrochemistry of Diazonium Salts

Aromatic diazonium salts (ArN2+ X−) are easily synthesized in an acidic aqueous medium (HBF4) starting from an amine in the presence of NaNO2, and in an aprotic medium (ACN + HBF4 in ether) in the presence of t-butylnitrite or in ACN + NOBF4 [1–2]. As many aromatic amines are available commercially, the preparation of a large number of diazonium salts can be easily carried out. They can be isolated and characterized, but they can be used directly in the solution where they have been prepared [3].

The chemistry of aromatic diazonium salts [1, 4, 5] is dominated by the electrophilic character of the azo group; they react with aromatic amines and phenols to give azo dyes (C-coupling) that are important coloring materials [6]. Aliphatic diazonium salts are extremely unstable and up to now only a few examples of grafting on carbon black involving the diazonium salt of 2-aminoethanesulfonic acid and 4-bromobenzylamine have been reported [1, 7].

As we will see below, when a diazonium reacts with a surface, with a few reported exceptions, the diazonium group is lost and the radical reacts with the surface, therefore grafting involves a homolytic dediazonation step; in this respect the dediazonation reactions are important for discussing the grafting mechanism. This dediazonation can take place heterolytically to give Ar+ cations, or homolytically to give Ar. radicals [8]; these spontaneous reactions can be slowed down by reducing the temperature to below 5 °C. The Sandmeyer reaction (1.1) is a first example of an important dediazonation reaction involving a radical; the reduction of the diazonium salt by cupric chloride or bromide ArCl, (Br) gives an aryl radical that abstracts a chlorine (bromine) atom from CuCl (Br) to give ArCl (Br), as shown in the reaction.

 (1.1)

A second important dediazonation reaction of diazonium salts in relation to grafting is the Gomberg–Bachman reaction; in the presence of a base the diazonium group is lost to give radicals that couple to other aromatic groups, dimers and a number of other coupling products are obtained [9, 10]. The Pschorr reaction is the intramolecular reaction of an aryl radical with an aryl group, the radical is produced, for example, by reduction of a diazonium salt by Cu(0) [11]. Merweein reactions also rely on the formation of radicals [12]. Solvolytic dediazonations are another example, they can take place in a heterolytic or homolytic manner, that is, through the intermediacy of an aryl cation or an aryl radical [13–17]; heterolytic dediazonation takes place in solvents of low nucleophilicity (H2O), while a homolytic mechanism is observed in solvents of increased nucleophilicity (HMPT, pyridine), in a number of solvents, such as MeOH, EtOH, DMSO, both mechanisms can be observed [14]. For example, in ethanol a slow heterolytic mechanism is observed in an acid medium and a 50 times faster homolytic one in a basic medium [14]. For a given solvent, electron-withdrawing substituents in the aromatic ring favor homolytic dediazoniations [14].

In an aqueous acidic medium and in aprotic non-nucleophilic solvents diazonium salts are present, but at neutral and basic pHs [13–17] equilibria between the diazohydroxide and diazoates are established; they are displaced toward the formation of diazoates; equilibrium and rate constants have been measured [13]. In the presence of alcohols, diazoethers Ar–NN–OEt [13, 18] , and in the presence of amines, triazenes Ar–NN-(NR) are obtained. These derivatives can also be used for surface modification. For example, diazohydroxides can spontaneously dediazonize and the ensuing radical attaches to the surface of gold [19]. Triazenes are interesting because they are transformed into diazonium salts in an acid medium; in 2% HF the oxidized silicon surface is transformed into Si–H and aryldiethyltriazenes are transformed into aryldiazonium salts, followed by spontaneous grafting of the aryl species to the silicon surface [20]. They can also generate aryldiazonium salts in the presence of electrogenerated acid produced by oxidation of hydrazine [21].