New Strategies in Chemical Synthesis and Catalysis E-Book

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

Seitenzahl: 651

Veröffentlichungsjahr: 2012

Beschreibung

This volume represents one of the two edited by inviting a selection of young researchers participating to the European Young Chemist
Award 2010. The other volume concerns the area of Nanotechnology/Material Science and is titled: Molecules at Work.
This book contains the contributions of selected young chemists from the field of synthetic chemistry. The contributions are grouped
under the three following umbrella topics:

Synthetic Methods
Catalysis
Combinatorial and Chemical Biology

This volume is an indispensable read for all organic and inorganic chemists, biochemists, chemists working with/on organometallics,
and Ph.D. students in chemistry interested in seeing what tomorrow's chemistry will look like.

Leseprobe

Table of Contents

Related Titles

Title Page

Copyright

Preface

List of Contributors

Part I: Synthetic Methods

Chapter 1: Electrospray and Cryospray Mass Spectrometry: From Serendipity to Designed Synthesis of Supramolecular Coordination and Polyoxometalate Clusters

1.1 Introduction

1.2 Background to ESI-MS

1.3 Application of High-Resolution ESI-MS and CSI-MS to Polyoxometalate Cluster Systems

1.4 Species Identification and Probing Structural Transformations in Multi-Metallic Systems

1.5 Future Challenges and Conclusions

References

Chapter 2: Efficient Synthesis of Natural Products Aided by Automated Synthesizers and Microreactors

2.1 Efficient Synthesis of Natural Products Aided by Automated Synthesizers

2.2 Continuous-Flow Synthesis of Vitamin D3

2.3 Conclusions

Acknowledgments

References

Chapter 3: Chemoselective Reduction of Amides and Imides

3.1 Introduction

3.2 Reduction of Tertiary Amides

3.3 Reduction of Secondary Amides

3.4 Dehydration of Primary Amides

3.5 Reduction of Imides

3.6 Conclusion

Acknowledgment

References

Chapter 4: Ionic Ozonides–From Simple Inorganic Salts to Supramolecular Building Blocks

4.1 The Forgotten Oxygen Anion

4.2 The Synthesis of Ionic Ozonides

4.3 The Structural Variety of Ionic Ozonides

4.4 Magnetic Properties

4.5 Conclusions and Perspectives

References

Chapter 5: Chemistry and Biological Properties of Amidinoureas: Strategies for the Synthesis of Original Bioactive Hit Compounds

5.1 Amidinoureas: an Introduction

5.2 Amidinoureas in Chemistry

5.3 Synthetic Strategies for the Preparation of Amidinoureas

5.4 Macrocyclic Amidinoureas

5.5 Perspectives

Acknowledgments

References

Part II: Catalysis

Chapter 6: DNA Catalysts for Synthetic Applications in Biomolecular Chemistry

6.1 Introduction

6.2 In vitro Selection of Deoxyribozymes

6.3 Scope of DNA-Catalyzed Reactions

6.4 Synthetic Applications of RNA-Cleaving Deoxyribozymes

6.5 DNA-Catalyzed Linear Ligation of RNA

6.6 DNA-Catalyzed Synthesis of 2′,5′-Branched Nucleic Acids

6.7 DNA-Catalyzed Synthesis of Nucleopeptide Conjugates

6.8 Mechanistic Aspects of DNA Catalysis

6.9 Conclusions and Outlook

References

Chapter 7: Iron-Catalyzed Csp3–H Oxidation with H2O2: Converting a Radical Reaction into a Selective and Efficient Synthetic Tool

7.1 Introduction and Scope

7.2 Environmentally Benign C–H Oxidation

7.3 Inspiration from Nature

7.4 Mechanistic Considerations

7.5 Bioinspired C–H Oxidation Catalysts

7.6 Perspectives

References

Chapter 8: Hydrogen Bonds as an Alternative Activation

8.1 Introduction

8.2 Thiourea Catalysts

8.3 Conclusions

Acknowledgments

References

Part III: Combinatorial and Chemical Biology

Chapter 9: Electrosynthesized Structured Catalysts for H2 Production

9.1 Introduction

9.2 Preparation of Structured Catalysts

9.3 Electrosynthesis

9.4 Electrosynthesis of Hydrotalcite-Type Compounds

9.5 Summary and Outlook

References

Chapter 10: Microkinetic Analysis of Complex Chemical Processes at Surfaces

10.1 Introduction

10.2 Time and Length Scales in Heterogeneous Catalysis

10.3 Hierarchical Multiscale Approach for Microkinetic Model Development

10.4 Show Case: Microkinetic Analysis of CH4 Partial Oxidation on Rh

10.5 Conclusions

Acknowledgments

References

Chapter 11: Synthetic Potential behind Gold-Catalyzed Redox Processes

11.1 Introduction

11.2 Gold-Catalyzed Reactions Involving Oxygen Functionalities

11.3 Gold-Catalyzed Reactions Involving Nitrogen Functionalities

11.4 Gold-Catalyzed Reactions Involving C–C Bond Formation

11.5 Gold-Catalyzed Reactions Involving Alkene Difunctionalization

11.6 Gold-Catalyzed Reactions Involving Halogen Functionalities

11.7 Summary and Outlook

References

Chapter 12: Transition-Metal Complexes in Supported Liquid Phase and Supercritical Fluids–A Beneficial Combination for Selective Continuous-Flow Catalysis with Integrated Product Separation

12.1 Strategies for Catalyst Immobilization Using Permanent Separation Barriers

12.2 Supported Liquid-Phase Catalysts Based on Organic Solvents (SLP)

12.3 Supported Aqueous-Phase Catalysts (SAP)

12.4 Supported Ionic Liquid-Phase Catalysts (SILP)

12.5 Supported Liquid-Phase Catalysts and Supercritical Fluids

12.6 Conclusion

References

Chapter 13: Inhibiting Pathogenic Protein Aggregation: Combinatorial Chemistry in Combating Alpha-1 Antitrypsin Deficiency

13.1 Introduction

13.2 α1-Antitrypsin Deficiency

13.3 Targeting the s4A Site with the Peptide Annealing Method

13.4 Expanding the Molecular Diversity

13.5 Characterization of the Combinatorially Selected Peptide

13.6 Conclusion and Outlook

Acknowledgments

References

Chapter 14: Synthesis and Application of Macrocycles Using Dynamic Combinatorial Chemistry

14.1 Supramolecular Chemistry

14.2 Dynamic Combinatorial Chemistry

14.3 Ion Transport across Membranes Mediated by a Dynamic Combinatorial Library

References

Chapter 15: Toward Tomorrow's Drugs: the Synthesis of Compound Libraries by Solid-Phase Chemistry

15.1 Introduction

15.2 Solid-Phase Synthesis of Selected Privileged Structures

15.3 Conclusions and Outlook

Acknowledgment

References

Index

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The Editors

Prof. Bruno Pignataro

Università di Palermo

Dipartimento di Chimica

“S. Cannizzaro”

Viale delle Scienze ed. 17

90128 Palermo

Italy

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

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Preface

The international scenario of chemical research, alongside the development of the traditional areas of chemistry, sees a growing development of those areas of chemistry that are multi- and cross-disciplinary dealing more and more with recent challenges and opportunities in chemistry. The focus of interest is always our global society and its “healthy” and sustainable future.

The aim of the most advanced meetings in chemistry is often to have a better quality of life for all people and to showcase knowledge, advanced products, and services which improve the efficiency of chemical professionals, the local and global environment and our well-being. As shown in the last conference of the European Association for Chemical and Molecular Sciences—3rd EuCheMs Chemistry Congress in Nürnberg (29 August to 2 September 2010)—chemistry is considered “a creative force” and scientists are convinced that it will shape the future.

In the road map for the development of chemistry you can find different trends (see, for instance, the document “Chemistry: Developing Solutions in a Changing World” produced by EuCheMs). One of these is related to the fact that the advancement in molecular design and its control becomes more complete. Chemists engineer their synthetic products more and more on the molecular scale exploiting and guiding in an increasingly controlled manner not only the strong bond but also the weak bonds (π − π interaction, metal ligand coordination, hydrogen bonds, hydrophobic interactions, van der Waals interactions, etc.). Taking into account that Nature still has a lot of things to teach us for preparing useful chemical systems, in this trend one can find the effort to close the gap between synthetic and natural products. This even if we must here stress the fact that those systems chemists can create may have characteristics or properties that are present or not in nature!

The present synthetic efforts in this area of chemistry are directed at overcoming self-assembling and obtaining control over the kinetic instability of the covalent architectures going from self-assembling to the far-from-equilibrium self-organization. This is in order to have molecular superstructures with particular well-defined conformations and therefore functions.

In connection with the advancements in understanding the phenomena and behaviors at molecular level, another trend in the development of chemical science sees an increasing tendency to look, in a more and more different manner, to the properties and reactions of the chemical systems also in order to throw further bridges between Chemistry and other disciplines such as Molecular Biology, Electronics, or Material Science. The power of synthetic methods directed at obtaining new functional nanosystems is now well documented and the products of such synthetic efforts embrace a large spectrum of sophisticated applications such as gene transfection, catalysis, lithium storage or sensors, and, in general, materials science and technology for a variety of applications.

In addition, learning also from the behavior of green plants, a research line is developing molecular photovoltaic devices having power conversion efficiencies of the order of 10%. This brings us closer to identifying “environmentally friendly” solutions for the world energy problem.

Another very important international trend follows from the fact that new discoveries and technological advancements improve our capacity to obtain better and better spatial, temporal, and energy resolutions. This is for one of these quantities alone or for these quantities in combination. In various fields, we are close to achieving physical limits. One astonishing recent achievement, which exploits these improved capacities, is, for instance, that reported by Paul Corkum, who launched at Ottawa the attosecond science. These researches showed that we can measure electronic orbitals and we might film the orbital modification during a photochemical reaction. This area of research then passes from femtochemistry led by Ahamed Zewail, allowing for the production of movies of the rupture and formation of chemical bonds, to this type of measures where theory and experiment are more and more interwoven. In addition, today we have the ability to measure smaller and smaller weights or other physical quantities such as picojoules, piconewtons, fractions of nanometer, femtograms, femtoamperes, kilodaltons, and so on with always increasing facility and reliability.

Jumping from the nanoscopic to the macroscopic world and to complex systems, the number of data that computers are able to manage continues to increase in a dramatic way. The impact of computational methods has become extraordinarily important in the development of science and technology. Simulations that were unthinkable a few years ago are now possible and allow us to start thinking about extremely complex predictions.

Just to finish this survey, in the frontier area with Life Sciences the challenges that chemists had sought a few years ago seem less and less ambitious and it appears more and more clear that chemistry plays an essential role in understanding life itself.

This book is placed in this international scenario. In particular, it represents one of the two books comprising contributions of selected scientists from the last edition of the European Young Chemist Award (EYCA 2010) presented during the 3rd EuCheMS Chemistry Congress. It is aimed to cover the generic area of chemical synthesis and catalysis while the other book encloses contributions from the area of material chemistry and is entitled “Molecules at work: SelfAssembly, NanoMaterials, and Molecular Machinery.”

As for the EYCA 2010, it was the third time this Award has been given. The aim of EYCA is to showcase and recognize the excellent research being carried out by young scientists working in the chemical sciences. In particular, it is intended to honor and encourage younger chemists whose current research displays a high level of excellence and distinction. It seeks to recognize and reward younger chemists (less than 35 years old) of exceptional ability who show promise for substantial future achievements in chemistry-related research fields.

The applications presented by the best candidates during the two previous editions of the Award were so stimulating that together with Wiley, EuCheMs, SCI, RSC, and GDCh, I decided to collect them into books. Thus, from the first edition of the Award was published the book Tomorrow's Chemistry today: Concept in Nanoscience, Organic Materials, and Environmental Chemistry (Wiley 2009) and from the second edition of the Award the three books (Wiley 2010) entitled Ideas in Chemistry and Molecular Sciences: Advances in Synthetic Chemistry, Ideas in Chemistry and Molecular Sciences: Where Chemistry meets Life, and Ideas in Chemistry and Molecular Sciences: Advances in Nanotechnology, Materials, and Devices.

The work from this third edition of the Award was once more very stimulating and again pushed by Wiley, EuCheMs, SCI, RSC, and GDCh, I planned to collect the best contributions into two books.

The scientific standing of the award applicants was undoubtedly very high and their research achievements are remarkable, especially in relation to their young age. In the guest editorial published by me “Chemistry: A European Journal” (vol. 16 (2010), pp. 13888–13893), I reported many details of the quality of the participants and of the whole Award Competition.

However, let me stress here some of points shown there. About 45% of the applicants have been chosen to give an oral presentation to the Nürnberg Congress. Among the participants one can find candidates with about 60 papers in peer-reviewed international journals and guiding a group of more than 20 PhDs and Post Docs, or candidates whose works got more than 1500 citations. The publication lists of most applicants proudly included the appearance of their work in the leading general science/chemistry journals such as Science, Nature, Angewandte Chemie, Journal of the American Chemical Society, and so on or the best niche journals in the fields of organic, inorganic, organometallic, physical, analytical, environmental, and medicinal chemistry. Several participants have been granted different prizes, have been invited to give different lectures, and achieved further recognitions such as front-end covers, hot articles, or highlights in top journals. Moreover, reading the application documents it comes out clearly that many of the competitors have different scientific interests and do have very exciting ideas for their future work. Further support for the applications, and a testament to the very high quality of the competitors, was apparent from the comments contained in the often very effusive recommendation letters coming from a number of eminent scientists. A flavor of these from the applications received can be found in the above cited guest editorial published by “Chemistry: A European Journal.”

This is the pool from which I fished the contributors of the above two books, and of this book in particular.

In fact, this book gives an account of the most recent results of research in Organic, Inorganic, and Organometallic Synthesis as well as in Catalysis, based on a selection of work by leading young scientists. The authors provide the state of the art in their field of research and a perspective or preview of the future research directions.

The content covers some of the aspects of the international chemical research highlighted above. The book is divided into three parts dedicated to the Synthetic Methods, Catalysis, and Combinatorial and Chemical Biology, even if in some cases the content of one part may overlap that of another.

Part I begins with two new synthetic strategies.

The first deals with high-resolution time-of-flight mass spectrometry (TOF-MS), which, over the last decade, has been employed in an effort to throw light upon assembly–disassembly processes of polyoxometalate (POM) and coordination clusters and to identify novel reactive and intermediate species in reaction mixtures as well. The most recent developments of this type of application of mass spectrometry are discussed, showing that this strategy contributes to opening the door for further exploration, discoveries, and well-established designing methodologies toward materials with predefined functionalities.

The second synthetic strategy deals with automated synthesizers explaining how these may help synthetic chemists to prepare natural products. In particular, it is shown that the use of such systems eliminates wastage of time with the trivial, repetitive, and long steps of the traditional synthetic procedure and thereby gives the opportunity to expend more time on the advanced and challenging work of developing new synthetic routes for the total synthesis of natural products.

Ionic ozonides and amidoureas are the themes of two other chapters of Part I. In particular, Chapter 4 describes part of the investigations on ionic ozonides that have been performed over the last decades, focusing on the synthesis and structure–property relationships. In agreement with the authors, I hope that the chapter will motivate the reader to delve into this fascinating field of molecular inorganic chemistry.

Chapter 5, dealing with the very interesting field of the chemistry of amidinoureas, is entitled “Chemistry and biological properties of amidinoureas: strategies for the synthesis of original bioactive hit compounds” and concludes that “the race for amidinoureas has just started and their full potential has still to be discovered.” There is again a clear invitation to the reader to shift some of his/her interest to this field.

Chapter 3 reports on the catalytic chemoselective reduction of amides and imides to the corresponding amines by using the hydrosilylation strategy and is therefore, in some respect, a bridge to the contributions reported in Part II.

Part II is specifically dedicated to catalysis. Again, the themes treated are very different and cover a wide area of the world of catalysis.

In particular, Chapter 8 details a contribution in the huge field of organocatalysis in general and chiral thioureas in particular. Different thiourea-catalyzed processes have been shown. Some of them are original and pioneering in this area and became a framework for further reactions to be explored.

Moving on to a different aspect of catalytic applications, Chapter 9 shows that electrosynthesis has several advantages for the coating of metallic supports. This study demonstrated the feasibility of the electrosynthesis of HT compounds (lamellar compounds with chemical formula [M2 + 1 − xM3 + x(OH)2](An − x/n)nH2O) to coat metallic foams leading to structured catalysts. The growth and composition of the coating are controlled by varying the deposition time, applied potential, and bath composition.

The overview of the state-of-the-art approach to the microkinetic analysis of complex chemical processes is provided in Chapter 10. At first, a general overview of the hierarchical multiscale approach for the microkinetic modeling and analysis of complex chemical processes at surfaces is given. Then, the results on the microkinetic modeling and analysis of the partial oxidation of methane on Rh catalysts are reviewed.

The focus of Chapter 11 is to review gold-catalyzed redox processes and their synthetic impact. Due to the fact that the field is rather wide, the chapter is just focused on homogeneous catalysis, skipping the heterogeneous methodologies. In agreement with the authors I hope that “even if key contributions have been left out, those that are included give the reader an overview of the targets already achieved as well as the new trends and challenges still ahead in the fascinating area of gold-catalyzed redox processes.”

Transition Metal Complexes in Supported Liquid Phase (SLF) is the topic of Chapter 12. Dispersion of a concentrated catalyst solution on the surface of a porous substrates has the respective advantages of liquid- and solid-phase immobilization. In agreement with the authors it is possible to say that the examples summarized in this chapter shows that SLPs represent a versatile and successful approach to organometallic catalyst recovery and recycling. This is particularly interesting with the use of nanoscale or molecular catalysts under continuous-flow.

The last two chapters collected in this section are at least in some respect connected to the chemical biology and build therefore a bridge to the third part of this book.

The aim of Chapter 7 is to review the development of bioinspired iron catalysts for unactivated Csp3E–H oxidation over the last two decades, and to investigate the important points for the design of efficient and selective catalysts.

Chapter 6 deals with DNA catalysts for synthetic applications in biomolecular chemistry. The focus is on deoxyribozymes as only one partial feature of DNA's applications in current chemical research. In the chapter, a brief overview of the scope of reactions catalyzed by deoxyribozymes is followed by selected examples of DNA catalysts for the preparation of biomolecules that are challenging to be approached by other methods. The major emphasis is on DNA enzymes that enable the ligation of nucleic acid fragments in different topologies.

Part III is dedicated to Combinatorial and Chemical Biology. There are three chapters in this part.

Chapter 13 is just at the interface of chemistry and biology and deals with inhibiting pathogenic protein aggregation.

Chapter 14 entitled “Synthesis and Application of Macrocycles Using Dynamic Combinatorial Chemistry” reports on the ion transport across membranes mediated by a dynamic combinatorial library.

The book closes with a review illustrating representative examples of solid-phase-generated libraries including their evaluation against various biological targets in Chapter 15. As pointed out by the authors, the latter are mainly members of the G-protein coupled receptors family, to which about half of all new drugs belong. The selected syntheses are organized by their respective privileged substructures. An overview of different reaction conditions and linkers used in solid-phase chemistry is also given.

I feel that the book is of major interest to chemists in the organic, inorganic, and organometallic areas but also to material chemists.

It should be relevant for readers both from academia and industry since it deals with fundamental contributions and possible applications.

As I have done for the other books of this series, I cannot finish this preface without acknowledging all the authors and all the persons who helped and supported me in this project. In particular, I would like to thank Prof. Giovanni Natile, Prof. Francesco De Angelis, and Prof. Luigi Campanella, who, as Presidents of the Italian Chemical Society and/or EuCheMs representatives, strongly encouraged me during the years in this activity. And of course, I thank all those Societies (see the book cover) that motivated and supported the book.

Palermo

Bruno Pignataro

January 2012

List of Contributors

Francesco Basile

ALMA MATER STUDIORUM-Università di Bologna

Dip. Chimica Industriale e dei Materiali

Viale Risorgimento 4

40136 Bologna

Italy

Patricia Benito

ALMA MATER STUDIORUM-Università di Bologna

Dip. Chimica Industriale e dei Materiali

Viale Risorgimento 4

40136 Bologna

Italy

Stefan Bräse

Institute of Organic Chemistry

Karlsruhe Institute of Technology (KIT)

Fritz-Haber-Weg 6

D-76131 Karlsruhe

Germany

Daniele Castagnolo

University of Siena

Dipartimento Farmaco Chimico Tecnologico

Via Alcide de Gasperi 2

53100 Siena

Italy

Yi-Pin Chang

University of Oxford

Department of Chemistry

Mansfield Road

Oxford OX1 3TA

UK

Tamilselvi Chinnusamy

Institut für Technische und Makromolekulare Chemie

RWTH Aachen University

Worringerweg 1

52074 Aachen

Germany

Leroy Cronin

The University of Glasgow

School of Chemistry

University Avenue

Glasgow G12 8QQ

UK

Shoubhik Das

Leibniz-Institut für Katalyse e.V. an der Universität Rostock

Albert-Einstein-Str. 29a

18059 Rostock

Germany

Giuseppe Fornasari

ALMA MATER STUDIORUM-Università di Bologna

Dip. Chimica Industriale e dei Materiali

Viale Risorgimento 4

40136 Bologna

Italy

Shinichiro Fuse

Tokyo Institute of Technology

Department of Applied Chemistry

2-12-1-H-101 Ookayama Meguro-ku

Tokyo 152-8552

Japan

Laura Gómez

Universitat de Girona

Departament de Química

Campus de Montilivi

17071 Girona

Spain

Teresa de Haro

University of Zürich

Organic Chemistry Institute

Winterthurerstrasse 190

CH-8057 Zürich

Switzerland

Raquel P. Herrera

ARAID, Fundación Aragón I+D

E-50004 Zaragoza

Spain

and

CSIC-Universidad de Zaragoza

Departamento de Química Org´nica

Instituto de Síntesis Química y Catílisis Homogénea (ISQCH)

C/Pedro Cerbuna

12 E-50009 Zaragoza

Spain

Ulrich Hintermair

Institut für Technische und Makromolekulare Chemie

RWTH Aachen University

Worringerweg 1

52074 Aachen

Germany

Claudia Höbartner

Research Group Nucleic Acid Chemistry

Max Planck Institute for Biophysical Chemistry

Am Fassberg 11

D-37077 Göttingen

Germany

Martin Jansen

Max Planck Institute for Solid State Research

Inorganic Solid State Chemistry

Heisenbergstr. 1

70569 Stuttgart

Germany

Dagmar C. Kapeller

Institute of Organic Chemistry

Karlsruhe Institute of Technology (KIT)

Hermann-von-Helmholtz-Platz 1

D-76344 Eggenstein-Leopoldshafen

Germany

Walter Leitner

Institut für Technische und Makromolekulare Chemie

RWTH Aachen University

Worringerweg 1

52074 Aachen

Germany

Matteo Maestri

Politecnico di Milano

Dipartimento di Energia

Laboratory of Catalysis and Catalytic Processes

Piazza Leonardo da Vinci 32

20133 Milano

Italy

Eugenia Marqués-López

CSIC-Universidad de Zaragoza

Departamento de Química Org´nica

Instituto de Síntesis Química y Cat´lisis Homogénea (ISQCH)

C/Pedro Cerbuna

12 E-50009 Zaragoza

Spain

Haralampos N. Miras

The University of Glasgow

School of Chemistry

University Avenue

Glasgow G12 8QQ

UK

Kazuhiro Machida

ChemGenesis Incorporated

Development Department

4-10-2 Nihonbashi-honcho

Chuo-ku

Tokyo 103-0023

Japan

Marco Monti

ALMA MATER STUDIORUM-Università di Bologna

Dip. Chimica Fisica e Inorganica

Viale Risorgimento 4

40136 Bologna

Italy

Cristina Nevado

University of Zürich

Organic Chemistry Institute

Winterthurerstrasse 190

CH-8057 Zürich

Switzerland

Hanne Nuss

Max Planck Institute for Solid State Research

Inorganic Solid State Chemistry

Heisenbergstr. 1

70569 Stuttgart

Germany

P. I. Pradeepkumar

Indian Institute of Technology Bombay

Department of Chemistry

Powai

Mumbai 400076

India

Vittorio Saggiomo

Centre for Systems Chemistry

Stratingh Institute

Faculty of Mathematics and Natural Sciences

University of Groningen

Nijenborgh 4

9747 AG Groningen

The Netherlands

Erika Scavetta

ALMA MATER STUDIORUM-Università di Bologna

Dip. Chimica Fisica e Inorganica

Viale Risorgimento 4

40136 Bologna

Italy

Domenica Tonelli

ALMA MATER STUDIORUM-Università di Bologna

Dip. Chimica Fisica e Inorganica

Viale Risorgimento 4

40136, Bologna

Italy

Takashi Takahashi

Tokyo Institute of Technology

Department of Applied Chemistry

2-12-1-H-101 Ookayama Meguro-ku

Tokyo 152-8552

Japan

Angelo Vaccari

ALMA MATER STUDIORUM-Università di Bologna

Dip. Chimica Industriale e dei Materiali

Viale Risorgimento 4

40136 Bologna

Italy

Part I

Synthetic Methods

Chapter 1

Electrospray and Cryospray Mass Spectrometry: From Serendipity to Designed Synthesis of Supramolecular Coordination and Polyoxometalate Clusters

Haralampos N. Miras and Leroy Cronin

1.1 Introduction

Molecular self-assembly is an exciting occurrence which governs how simple building blocks [1] can be organized spontaneously into complex architectures [2]. Such self-assembly processes are highly dependent upon the experimental conditions [3] often to such a degree that total control is never easily achieved [4]. This can be frustrating since extremely small changes in reaction conditions can yield totally different results [5]. For instance, many research groups have reported the discovery of new building blocks, architectures, and materials that exhibit fundamentally new and interesting properties as a result of the self-assembly process that were simply not expected [6]. The serendipitous result in self-assembled chemical systems usually lacks the element of design. On the other hand, little progress would be made if serendipity (i.e., chance discoveries) was the only guide [7]. Future work usually uses valuable information that is extracted by observations made from earlier studies and used as a starting point for a more designed approach. Representative examples that fall into the category of self-assembled chemical systems are the polynuclear coordination compounds and the polyoxometalate (POM) clusters.

POM clusters represent an unparalleled range of architectures and chemical properties, acting as a set of transferable building blocks that can be reliably utilized in the formation of new materials. These key features are being exploited rapidly today after a rise in popularity of POMs over the last two decades [8, 9]. Today, POM chemistry is an important, emerging area that promises to allow the development of sophisticated molecule-based materials and devices with numerous applications ranging from electronics and catalysis to physics [1013]. The reason for the explosion in the number of structurally characterized POM compounds is due to developments in instrumentation and novel synthetic approaches. In terms of technique development, fast and routine single-crystal data collection has allowed the area to accelerate to the point where the bottle neck has moved to structure refinement and crystallization of new compounds rather than the time taken for data collection and initial structure solution. However, despite all the promise, the relentless increase in the number of structures and derivatives mean that it can be difficult to distinguish between the different cluster types and subtypes, whereas till now it seemed hard to be sure that the processes that govern the self-assembly of these complex architectural systems can be fully controlled and directed.