Lanthanides and Actinides in Molecular Magnetism E-Book

Richard A. Layfield

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

Seitenzahl: 670

Veröffentlichungsjahr: 2015

Beschreibung

The first reference on this rapidly growing topic provides an essential up-to-date guide to current and emerging trends.
A group of international experts has been carefully selected by the editors to cover all the central aspects, with a focus on molecular species while also including industrial applications.
The resulting unique overview is a must-have for researchers, both in academia and industry, who are entering or already working in the field.

Leseprobe

Table of Contents

Cover

Related Titles

Title Page

Copyright

Preface

List of Contributors

Chapter 1: Electronic Structure and Magnetic Properties of Lanthanide Molecular Complexes

1.1 Introduction

1.2 Free Ion Electronic Structure

1.3 Electronic Structure of Lanthanide Ions in a Ligand Field

1.4 Magnetic Properties of Isolated Lanthanide Ions

1.5 Exchange Coupling in Systems Containing Orbitally Degenerate Lanthanides

Acknowledgements

References

Chapter 2: Mononuclear Lanthanide Complexes: Use of the Crystal Field Theory to Design Single-Ion Magnets and Spin Qubits

2.1 Introduction

2.2 Modelling the Magnetic Properties of Lanthanide Single-Ion Magnets: The Use of the Crystal Field Model

2.3 Magneto-Structural Correlations for Some Typical Symmetries

2.4 Impact of Lanthanide Complexes in Quantum Computing

2.5 Conclusions

Acknowledgements

References

Chapter 3: Polynuclear Lanthanide Single Molecule Magnets

3.1 Introduction

3.2 Synthetic Strategies

3.3 Conclusion

References

Chapter 4: Lanthanides in Extended Molecular Networks

4.1 Introduction

4.2 Extended Networks Based on Gd

3+

4.3 Extended Networks Based on Anisotropic Ions

4.4 Conclusions

References

Chapter 5: Experimental Aspects of Lanthanide Single-Molecule Magnet Physics

5.1 Introduction

5.2 Manifestation of Single-Molecule Magnet Behaviour

5.3 Quantifying the Magnetic Anisotropy

5.4 Splitting of the Ground Multiplet

5.5 Observation of the Signatures of Exchange Coupling

5.6 Concluding Remarks and Perspectives

References

Chapter 6: Computational Modelling of the Magnetic Properties of Lanthanide Compounds

6.1 Introduction

6.2

Ab Initio

Description of Lanthanides and its Relation to Other Methods

6.3

Ab Initio

Calculation of Anisotropic Magnetic Properties of Mononuclear Complexes

6.4

Ab Initio

Calculation of Anisotropic Magnetic Properties of Polynuclear Complexes

6.5 Conclusions

References

Chapter 7: Lanthanide Complexes as Realizations of Qubits and Qugates for Quantum Computing

7.1 Introduction to Quantum Computation

7.2 Quantum Computing with Electron Spin Qubits

7.3 Single Lanthanide Ions as Spin Qubits

7.4 Lanthanide Molecules as Prototypes of Two-Qubit Quantum Gates

7.5 Conclusions and Outlook

References

Chapter 8: Bis(phthalocyaninato) Lanthanide(III) Complexes – from Molecular Magnetism to Spintronic Devices

8.1 Introduction

8.2 Synthesis and Structure of LnPc

2

Complexes

8.3 Bulk Magnetism of LnPc

2

Complexes

8.4 Surface Magnetism of LnPc

2

Complexes

8.5 Molecular Spintronic Devices on the Base of [TbPc

2

]

0

SIMs

8.6 Conclusion and Outlook

Abbreviations

References

Chapter 9: Lanthanides and the Magnetocaloric Effect

9.1 Applications of Magnets

9.2 Cold Reasoning

9.3 Current Technologies

9.4 How Paramagnets Act as Refrigerants

9.5 More Parameters

9.6 Aims

9.7 Important Concepts for a Large Magnetocaloric Effect

9.8 High-Performance MCE Materials

9.9 Outlook

References

Chapter 10: Actinide Single-Molecule Magnets

10.1 Introduction

10.2 Literature Survey of Published Actinide Single-Molecule Magnets

10.3 Magnetic Coupling in Actinides

10.4 Conclusions

References

Index

EULA

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Guide

Cover

Table of Contents

Preface

Chapter 1: Electronic Structure and Magnetic Properties of Lanthanide Molecular Complexes

List of Illustrations

Figure 1.1

Figure 1.2

Figure 1.3

Figure 1.4

Figure 2.1

Figure 2.2

Figure 2.3

Figure 2.4

Figure 2.5

Figure 2.6

Figure 2.7

Figure 2.8

Figure 2.9

Figure 2.10

Figure 2.11

Figure 2.12

Figure 2.13

Figure 2.14

Figure 2.15

Scheme 3.1

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6

Figure 3.7

Figure 3.8

Figure 3.9

Figure 3.10

Figure 3.11

Figure 3.12

Figure 3.13

Figure 3.14

Figure 3.15

Figure 3.16

Figure 3.17

Figure 3.18

Figure 3.19

Figure 3.20

Figure 3.21

Figure 3.22

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 4.5

Figure 4.6

Figure 4.7

Figure 4.8

Scheme 4.1

Scheme 4.2

Figure 4.9

Figure 4.10

Scheme 4.3

Figure 4.11

Figure 4.12

Figure 4.13

Figure 4.14

Figure 4.15

Figure 5.1

Figure 5.2

Figure 5.3

Figure 5.4

Figure 5.5

Figure 5.6

Figure 5.7

Figure 5.8

Figure 5.9

Figure 5.10

Figure 5.11

Figure 5.12

Figure 5.13

Figure 5.14

Figure 6.1

Figure 6.2

Figure 6.3

Figure 6.4

Figure 6.5

Figure 6.6

Figure 6.7

Figure 6.8

Figure 6.9

Figure 7.1

Figure 7.2

Figure 7.3

Figure 7.4

Figure 7.5

Figure 7.6

Figure 7.7

Figure 7.8

Figure 7.9

Figure 7.10

Figure 7.11

Figure 7.12

Figure 7.13

Figure 7.14

Figure 7.15

Figure 7.16

Figure 7.17

Figure 7.18

Figure 7.19

Figure 8.1

Figure 8.2

Figure 8.3

Figure 8.4

Scheme 8.1

Scheme 8.2

Figure 8.5

Figure 8.6

Figure 8.7

Figure 8.8

Figure 8.9

Figure 8.10

Figure 8.11

Figure 8.12

Figure 8.13

Figure 8.14

Figure 8.15

Figure 8.16

Figure 8.17

Figure 8.18

Figure 8.19

Figure 8.21

Figure 8.20

Figure 9.1

Figure 9.2

Figure 9.3

Figure 9.4

Figure 9.5

Figure 9.6

Figure 9.7

Figure 9.8

Figure 9.9

Figure 9.10

Figure 10.1

Figure 10.2

Figure 10.3

Figure 10.4

Figure 10.5

Figure 10.6

Figure 10.7

Figure 10.8

Figure 10.9

Figure 10.10

List of Tables

Table 1.1

Table 1.2

Table 1.3

Table 2.1

Table 2.3

Table 2.4

Table 4.1

Table 4.2

Table 6.1

Table 6.2

Table 6.3

Table 6.4

Table 6.5

Table 8.1

Table 8.2

Table 9.1

Table 9.2

Table 10.1

Table 10.2

Related Titles

de Bettencourt-Dias, A. (ed.)

Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials

2014

Print ISBN: 978-1-119-95083-7

(Also available in a variety of electronic formats)

Gatteschi, D., Benelli, C.

Introduction to Molecular Magnetism

From Transition Metals to Lanthanides

2015

Print ISBN: 978-3-527-33540-4

(Also available in a variety of electronic formats)

Hilzinger, R., Rodewald, W.

Magnetic Materials

Fundamentals, Products, Properties, Applications

2013

Print ISBN: 978-3-895-78352-4

Edited by

Richard A. Layfield and Muralee Murugesu

Lanthanides and Actinides in Molecular Magnetism

The Editors

Dr. Richard A. Layfield

The University of Manchester

School of Chemistry

Oxford Road

M13 9PL Manchester

United Kingdom

Prof. Dr. Muralee Murugesu

University of Ottawa

Department of Chemistry/D'Iorio Hall

Marie Curie 10

ON K1N 6N NK

Canada

Cover

Periodic table: iStockphoto © Tomacco

Magnet: iStockphoto © jgroup

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Print ISBN: 978-3-527-33526-8

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Preface

A huge surge in the number of publications dealing with the magnetic properties of coordination compounds based on highly anisotropic lanthanide ions occurred in the past decade. This body of work provided the inspiration for the current book. In light of the recent trends, one could be forgiven for assuming that f-block magnetism is a new field of research: it is not, but there is no doubt that certain types of lanthanide and actinide compounds have breathed new life into an established field of molecular magnetism. In compiling Lanthanide and Actinides in Molecular Magnetism, our aim has been to set the scene by covering the important fundamental aspects of f-element electronic structure and magnetism and then to use this as a basis for understanding the most eye-catching recent developments and emerging cutting-edge topics. This aim has been achieved by the contributing authors, who address their chosen topics using a range of experimental and theoretical considerations, much of which is based on their own pioneering contributions to the field.

In Chapter 1, Sorace and Gatteschi deal with the fundamental aspects of lanthanide electronic structure and magnetism, and in Chapter 2, Clemente-Juan, Coronado and Gaita-Ariño develop a picture of how the crystal field theory can be used to design single-ion magnets and spin qubits. Tang and Zhang condense a huge volume of literature in Chapter 3 in order to cover the bewildering array of polynuclear lanthanide single-molecule magnets (SMMs), and extended molecular networks of lanthanide complexes are dealt with by Sessoli and Bernot in Chapter 4. The experimental aspects of SMM physics are covered by Pedersen, Woodruff, Bendix and Clérac in Chapter 5, and a detailed description of theoretical models of lanthanide magnetism is provided by Chibotaru and Ungur in Chapter 6. The promising role of lanthanide complexes in quantum computing is presented by Aromí, Luis and Roubeau in Chapter 7. Chapter 8 is a tour-de-force of lanthanide-phthalocyanine chemistry and physics authored by Lan, Klyatskaya and Ruben, from synthetic supramolecular chemistry to applications in molecular spintronic devices. The role of lanthanide complexes in the magnetocaloric effect is covered by Sharples and Collison in Chapter 9, and in Chapter 10, Liddle and van Slageren cover yet another emerging topic – namely, the applications of actinide elements in single-molecule magnetism.

One of the most exciting aspects of the material covered in this book is its multi-disciplinary nature: chemistry, physics, materials science and nanoscience all play their part. The potential applications in advanced technologies such as quantum computing add to the excitement. The beauty of this science is that it does not respect ‘traditional’ subject boundaries, which, the reader will find, is clearly demonstrated throughout. The target audience should span the full range of career stages. Established experts in the field will find the book to be an invaluable summary, while new research students will find it to be an excellent entry point to the wider literature. We hope that the book will become an indispensable guide for all scientists with interests in magnetism and in the magnetic properties of f-element compounds.

The editors owe a great debt of gratitude to the contributing authors, all of whom have invested significant time and effort in order to share their wisdom and insight.

The University of Manchester, UK

Richard Layfield

University of Ottawa, Canada

Muralee Murugesu

List of Contributors

Guillem Aromí

Universitat de Barcelona

Departament de Química Inorgànica

Grup de Magnetisme i Molècules Funcionals (GMMF)

Diagonal 645

Barcelona

Spain

Jesper Bendix

University of Copenhagen

Department of Chemistry

Universitetsparken 5

Copenhagen

Denmark

Kevin Bernot

Université Européenne de Bretagne

INSA, SCR, UMR 6226

Avenue des buttes de Coësmes CS70839

Rennes Cedex

France

Liviu F. Chibotaru

Katholieke Universiteit Leuven

Theory of Nanomaterials Group

Celestijnenlaan 200F

Heverlee

Belgium

Juan M. Clemente-Juan

Universidad de Valencia

Instituto de Ciencia Molecular

c/Catedrático José Beltrán, 2

Paterna

Spain

Rodolphe Clérac

CNRS, CRPP

UPR 8641

Pessac

France

and

University of Bordeaux

CRPP, UPR 8641

Pessac

France

David Collison

The University of Manchester

School of Chemistry

Oxford Road

Manchester M13 9PL

UK

Eugenio Coronado

Universidad de Valencia

Instituto de Ciencia Molecular

c/Catedrático José Beltrán, 2

Paterna

Spain

Alejandro Gaita-Ariño

Universidad de Valencia

Instituto de Ciencia Molecular

c/Catedrático José Beltrán, 2

Paterna

Spain

Dante Gatteschi

Università degli studi di Firneze

Laboratory for Molecular Magnetism

Dipartimento di Chimica

``Ugo Schiff'' and UdR INSTM

Via della Lastruccia 3

Sesto Fiorentino

Italy

Svetlana Klyatskaya

Karlsruher Institut für Technologie (KIT)

Institut für Nanotechnologie

Eggenstein-Leopoldshafen

Germany

Yanhua Lan

Karlsruher Institut für Technologie (KIT)

Institut für Nanotechnologie

Hermann-von-Helmholtz-Platz 1

Eggenstein-Leopoldshafen

Germany

Stephen T. Liddle

University of Nottingham

School of Chemistry

University Park

Nottingham NG7 2RD

UK

Fernando Luis

CSIC-Universidad de Zaragoza

Instituto de Ciencia de Materiales de Aragón

Pedro Cerbuna 12

Zaragoza

Spain

Kasper S. Pedersen

CNRS, CRPP

UPR 8641

Pessac

France

and

Univ Bordeaux

CRPP, UPR 8641

Pessac

France

and

University of Copenhagen

Department of Chemistry

Universitetsparken 5

Copenhagen

Denmark

Olivier Roubeau

CSIC-Universidad de Zaragoza

Instituto de Ciencia de Materiales de Aragón

Pedro Cerbuna 12

Zaragoza

Spain

Mario Ruben

Karlsruher Institut für Technologie (KIT)

Institut für Nanotechnologie

Hermann-von-Helmholtz-Platz 1

Eggenstein-Leopoldshafen

Germany

and

Université de Strasbourg

IPCMS-CNRS

23 Rue du Loess

Strasbourg

France

Roberta Sessoli

Università degli Studi di Firenze

Laboratory of Molecular Magnetism

Department of Chemistry and INSTM

Via della Lastruccia 3

Sesto Fiorentino

Italy

Joseph W. Sharples

School of Chemistry

The University of Manchester

Oxford Road

Manchester M13 9PL

UK

Joris van Slageren

Universität Stuttgart

Institut für Physikalische Chemie

Pfaffenwaldring 55

Stuttgart

Germany

Lorenzo Sorace

Università degli studi di Firneze

Laboratory for Molecular Magnetism

Dipartimento di Chimica

``Ugo Schiff'' and UdR INSTM

Via della Lastruccia 3

Sesto Fiorentino

Italy

Jinkui Tang

Chinese Academy of Sciences

State Key Laboratory of Rare Earth Resource Utilization

Changchun Institute of Applied Chemistry

Changchun, 130022

R. China

Liviu Ungur

Katholieke Universiteit Leuven

Theory of Nanomaterials Group

Celestijnenlaan 200F

Heverlee

Belgium

Daniel N. Woodruff

CNRS, CRPP

UPR 8641

Pessac

France

and

University of Bordeaux

CRPP, UPR 8641

Pessac

France

Peng Zhang

Chinese Academy of Sciences

State Key Laboratory of Rare Earth Resource Utilization

Changchun Institute of Applied Chemistry

Changchun, 130022

R. China

1Electronic Structure and Magnetic Properties of Lanthanide Molecular Complexes

Lorenzo Sorace and Dante Gatteschi

1.1 Introduction

The first studies on the magnetic and electronic properties of compounds containing lanthanide ions date back to the beginning of the twentieth century [1]. However, detailed investigation on these systems only began in the and helped set up an appropriate theoretical framework for the analysis of their properties [2–5]. Most of the studies reported in the early literature, which involved optical spectroscopy, magnetism, or electron paramagnetic resonance (EPR), were however concerned with inorganic systems in which the lanthanide occupied high symmetry sites, and paramagnetic ions were often doped in diamagnetic host lattices [6, 7].

On the other hand, the number of molecular complexes (which usually show a low point symmetry at the lanthanide site) whose magnetic properties had been well characterized remained quite small even in 1993, when Kahn [8] wrote his landmark book entitled Molecular Magnetism. The field of lanthanide molecular magnetism has indeed really boomed only in the last 15 years, when the availability of powerful theoretical and experimental techniques allowed deep insight into these systems. As a result, some more specific applications of the theory that was developed for inorganic systems to the molecular magnets case were needed. The purpose of this chapter is to describe the fundamental factors affecting the electronic structure of lanthanide complexes, with some specific focus on the symmetry, and the way this is related to their static magnetic properties (dynamic magnetic properties being the focus of a subsequent chapter).

Lanthanide atoms in the electronic ground state are characterized by the progressive filling of 4f shells, with the general configuration (with the exception of La, Ce, Gd, Lu, for which the ground configuration is ). For this reason, the most stable lanthanide ions are the tripositive ones, obtained by loss of the 5d and 6s electrons (notable exceptions are , and , which have stable electronic configurations). In the following, we discuss the paramagnetic properties of rare earth compounds arising from the unpaired 4f electrons: since these are effectively shielded by the completely filled 5s and 5p orbitals, their behaviour is much less affected by the coordination environment of the ion compared to the 3d transition metal series. Consequently, optical spectra consist of very sharp, weak lines due to formally forbidden 4f–4f transitions, while the magnetic properties can, to a first approximation, be expressed as those of a free