Electrochemistry of Functional Supramolecular Systems

With contributions from the most prominent experts around the world, this resource provides an accessible summary of electrochemical techniques and the applications of electrochemical concepts to molecular-level systems. It describes the most important electro-active functional supramolecular systems developed so far, including rotaxanes and catenanes as molecular machines and as elements for information processing; dendrimers as molecular batteries, sensors, light harvesting antennae, and drug delivery systems; and bio-hybrid devices.

Preface to the Wiley Series on Electrocatalysis And Electrochemistry vii

Foreword ix

Preface xi

Contributors xiii

1. Electrochemically Controlled H-Bonding 1
Diane K. Smith

2. Molecular Motions Driven by Transition Metal Redox Couples: Ion Translocation and Assembling– Disassembling of Dinuclear Double-Strand Helicates 33
Valeria Amendola and Luigi Fabbrizzi

3. Molecular Encapsulation of Redox-Active Guests 59
Angel E. Kaifer

4. Dendritic Encapsulation of Redox-Active Units 87
Christopher B. Gorman

5. Redox-Active Metal–Polypyridine Dendrimers as Light-Harvesting Antennae 121
Fausto Puntoriero, Scolastica Serroni, Francesco Nastasi, and Sebastiano Campagna

6. Dendrimers as Multielectron Storage Devices 145
Paola Ceroni and Margherita Venturi

7. Self-assembled Monolayers and Multilayers of Electroactive Thiols 185
Ibrahim Yildiz, Françisco M. Raymo and Massimiliano Lamberto

8. Electrochemistry of Carbon Nanoparticles 201
Luis Echegoyen, Amit Palkar, and Frederic Melin

9. Molecular Devices Based on Fullerenes and Carbon Nanotubes 229
Matteo Iurlo, Demis Paolucci, Massimo Marcaccio, and Francesco Paolucci

10. Functional Electroactive Biomolecules 261
Xiaomin Bin, Piotr Michal Diakowski, Kagan Kerman, Heinz-Bernhard Kraatz

11. Functional Nanoparticles as Catalysts and Sensors 301
Brian J. Jordan, Chandramouleeswaran Subramani, and Vincent M. Rotello

12. Biohybrid Electrochemical Devices 333
Ran Tel-Vered, Bilha Willner, and Itamar Willner

13. Electroactive Rotaxanes and Catenanes 377
Alberto Credi and Margherita Venturi

14. Electrochemically Driven Molecular Machines Based on Transition-metal Complexed Catenanes and Rotaxanes 425
Jean-Paul Collin, Fabien Durola, and Jean-Pierre Sauvage

15. Electroactive Molecules and Supramolecules for Information Processing and Storage 447
Guanxin Zhang, Deqing Zhang, and Daoben Zhu

16. Electrochemiluminescent Systems as Devices and Sensors 477
Andrzej Kapturkiewicz

17. Recent Developments in the Design of Dye-Sensitized Solar Cell Components 523
Stefano Caramori and Carlo Alberto Bignozzi

Index 581

"There is a strong combination here of structural considerations, redox schemes, and experimental data that should allow researchers in allied areas to make new connections with unfamiliar electrochemical techniques and strategies that may prove useful in their own work." (JACS, 2010)

Paola Ceroni, PhD, is Associate Professor at the University of Bologna. Dr. Ceroni's research focuses on the photochemistry and electrochemistry of molecular and supramolecular systems, with particular emphasis on photoactive dendrimers. Dr. Ceroni is coauthor of approximately 100 scientific papers.

Alberto Credi, PhD, is Associate Professor of Chemistry at the University of Bologna. Dr. Credi is particularly interested in the development of molecular machines, and has coauthored about 160 scientific papers in the fields of molecular and supramolecular photochemistry and electrochemistry. He is also the coauthor of the monograph Molecular Devices and Machines and of a handbook of photochemistry.

Margherita Venturi is Professor of Chemistry at the University of Bologna. From 1972 to 1991, she worked at the National Research Council of Bologna, studying the electron-transfer processes involved in model systems for the conversion of solar energy. Professor Venturi's present research focuses on the field of supramolecular photochemistry and electrochemistry. She is coauthor of about 180 articles, including several reviews. She is also the coauthor of the monograph Molecular Devices and Machines.

New breakthroughs in characterizing and operating supramolecular systems using electrochemical techniques

The marriage of electrochemistry and supramolecular chemistry has produced many new and interesting molecular-level devices and functions. Moreover, it has built a wealth of new scientific knowledge, offering the promise of practical applications in energy conversion, information and communication technologies, advanced materials, diagnostics, and medicine. This contributed work features 17 articles that highlight recent achievements in electrochemical research as applied to multi-component chemical systems, with particular emphasis on properties and functions. It highlights the accomplishments that can be achieved through the collaboration of electrochemists and supramolecular chemists.

Contributed by leading experts working at the interface of electrochemisty and supramolecular science, the book begins with basic investigations into systems in solution, followed by chapters dealing with less conventional multi-component architectures and environments. Finally, the book explores devices and systems of high complexity that offer the possibility of new, useful applications. Among the important electro-active functional systems presented are:

• Rotaxanes and catenanes as molecular machines and as elements for information processing

• Dendrimers as molecular batteries, sensors, light harvesting antennae, and drug delivery systems

• Nanoparticles, nanotubes, and monolayers

• Bio-hybrid devices

Most chapters begin with a discussion of the relevant basic concepts, making them accessible to non-specialists. References guide readers to the primary literature for further in-depth investigations of individual topics.

This book is recommended for all researchers and students interested in exploring electrochemistry at its frontiers with supramolecular chemistry, materials science, and biochemistry.