122 Structure and Bonding

Transcription

1 122 Structure and Bonding Series Editor: D. M. P. Mingos Editorial Board: P.Day T.J.Meyer H.W.Roesky J.-P.Sauvage

2 Structure and Bonding Series Editor: D. M. P. Mingos Recently Published and Forthcoming Volumes Single-Molecule Magnets and Related Phenomena Volume Editor: Winpenny, R. Vol. 122, 2006 Non-Covalent Multi-Porphyrin Assemblies Synthesis and Properties Volume Editor: Alessio, E. Vol. 121, 2006 Recent Developments in Mercury Sience Volume Editor: Atwood, David A. Vol. 120, 2006 Layered Double Hydroxides Volume Editors: Duan, X., Evans, D. G. Vol. 119, 2005 Semiconductor Nanocrystals and Silicate Nanoparticles Volume Editors: Peng, X., Mingos, D. M. P. Vol. 118, 2005 Magnetic Functions Beyond the Spin-Hamiltonian Volume Editor: Mingos, D. M. P. Vol. 117, 2005 Intermolecular Forces and Clusters II VolumeEditor:Wales,D.J. Vol. 116, 2005 Intermolecular Forces and Clusters I VolumeEditor:Wales,D.J. Vol. 115, 2005 Superconductivity in Complex Systems Volume Editor: Müller, K. A. Vol. 114, 2005 Principles and Applications of Density Functional Theory in Inorganic Chemistry II Volume Editors: Kaltsoyannis, N., McGrady, J. E. Vol. 113, 2004 Principles and Applications of Density Functional Theory in Inorganic Chemistry I Volume Editors: Kaltsoyannis, N., McGrady, J. E. Vol. 112, 2004 Supramolecular Assembly via Hydrogen Bonds II Volume Editor: Mingos, D. M. P. Vol. 111, 2004 Applications of Evolutionary Computation in Chemistry Volume Editors: Johnston, R. L. Vol. 110, 2004 Fullerene-Based Materials Structures and Properties Volume Editor: Prassides, K. Vol. 109, 2004 Supramolecular Assembly via Hydrogen Bonds I Volume Editor: Mingos, D. M. P. Vol. 108, 2004 Optical Spectra and Chemical Bonding in Transition Metal Complexes Special Volume II dedicated to Professor Jørgensen Volume Editor: Schönherr, T. Vol. 107, 2004

3 Single-Molecule Magnets and Related Phenomena Volume Editor: Richard Winpenny With contributions by G. Aromí B. Barbara E. K. Brechin A. Caneschi R. Clérac A. Cornia A. F. Costantino C. Coulon J. Curély D. Gatteschi T. Mallah M. Mannini E. J. L. McInnes H. Miyasaka J.-N. Rebilly R. Sessoli L. Zobbi 123

4 The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table. It focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. As a rule, contributions are specially commissioned. The editors and publishers will, however, always be pleased to receive suggestions and supplementary information. Papers are accepted for Structure and Bonding in English. In references Structure and Bonding is abbeviated Struct Bond andis cited as a journal. Springer WWW home page: springer.com Visit the Struct Bond content at springerlink.com Library of Congress Control Number: ISSN ISBN Springer Berlin Heidelberg New York ISBN Springer Berlin Heidelberg New York DOI /b This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable for prosecution under the German Copyright Law. Springer is a part of Springer Science+Business Media springer.com c Springer-Verlag Berlin Heidelberg 2006 Printed in Germany The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Cover design: Design & Production GmbH, Heidelberg Typesetting and Production: LE-TEX Jelonek, Schmidt& VöcklerGbR, Leipzig Printed on acid-free paper 02/3100 YL

5 Series Editor Prof. D. Michael P. Mingos Principal St. Edmund Hall Oxford OX1 4AR, UK Volume Editor Prof. Richard Winpenny Department of Chemistry The University of Manchester Oxford Road Manchester M13 9PL, UK Editorial Board Prof. Peter Day Director and Fullerian Professor of Chemistry The Royal Institution of Great Britain 21 Albermarle Street London W1X 4BS, UK Prof. Thomas J. Meyer Department of Chemistry Campus Box 3290 Venable and Kenan Laboratories The University of North Carolina and Chapel Hill Chapel Hill, NC , USA Prof. Herbert W. Roesky Institut for Anorganic Chemistry University of Göttingen Tammannstr Göttingen, Germany hroesky@gwdg.de Prof. Jean-Pierre Sauvage Faculté de Chimie Laboratoires de Chimie Organo-Minérale Université Louis Pasteur 4, rue Blaise Pascal Strasbourg Cedex, France sauvage@chimie.u-strasbg.fr

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9 Preface In some ways the story of single-molecule magnets (SMMs) starts with work performed in the Christou group during the 1980s. The research was dedicated to the synthesis of model compounds of the oxygen-evolving complex in Photosystem II. The work resulted in a very large number of polymetallic mixed-valent manganese complexes being made many having rather more metal centres than are strictly speaking required for an accurate representation oftheactivesiteoftheenzyme. The work had produced many beautiful model compounds and was very well reviewed at the time [1], but lacked a model for the highest oxidation state of the biological cycle. In attempting to make such a model by oxidation of manganese acetate with permanganate, a compound of formula [Mn 12 O 12 (O 2 CPh) 16 (H 2 O) 4 ] was isolated [2]. This was a new compound, but rather surprisingly it had a very close precedent: in 1980 Lis had made [Mn 12 O 12 (O 2 CMe) 16 (H 2 O) 4 ] and published the crystal structure [3]. Lis also included preliminary magnetic measurements from K, but did not interpret them. Even more surprisingly the first proposal of a dodecanuclear manganese complex from this type of reaction was made in 1921 by Weinland and Fischer [4], although given the equipment available at the time Weinland and Fischer did not get the metal-to-ligand stoichiometry correct. The rediscovery by the Christou group was therefore serendipitous. Boydet al. measuredthemagnetic properties of [Mn 12 O 12 (O 2 CPh) 16 (H 2 O) 4 ] and deduced a spin ground state of S =14[2].Thisisincorrect,butthemistake is unsurprising in that the behaviour of this compound is unlike that of previously prepared high-spin molecules. At that time, the highest spin known for a molecule was S = 12, for a molecule reported by Gatteschi s group [5]. As a result of the paper by Boyd et al. the Gatteschi group reinvestigated the Lis compound by high-field magnetisation and high-frequency EPR spectroscopy. The resulting paper, published by Caneschi et al. in 1991 [6], describes the freezing of the magnetisation at low fields, and also explains this behaviour which is analogous to that of superparamagnets due to the negative axial anisotropy of the high-spin ground state of the compound. The ground state was found to be S = 10, and later measurements show that [Mn 12 O 12 (O 2 CPh) 16 (H 2 O) 4 ] also has an S = 10 ground state [7, 8]. The paper by Caneschi et al. [6] misses one trick: the term single-molecule magnet is not used, however this is now

10 X Preface how these molecules are universally known. Despite the lack of a snappy title this paper introduces many of the basic ideas underlying the physics of SMMs. These initial discoveries have provided physicists with ideal objects for studying quantum phenomena, such as tunnelling of magnetisation. This was first reported by Barbara and co-workers [9], and simultaneously by Friedman et al. [10]. Many following studies have been designed to understand these phenomena and the mechanism of tunnelling. The advantage in studying the physics of SMMs over particulate supraparamagnets is that coordination chemists can vary the physical properties of the quantum objects using the skills of a synthetic chemist. The result has been a remarkably large number of derivatives of Mn12. Reviews of the physics and the quantum phenomena of SMMs have been published previously [11, 12], therefore here we have concentrated on aspects that have not been reviewed. Aromi and Brechin explore synthetic routes to SMMs, covering the literature exhaustively until May McInnes has reviewed the spectroscopic studies of SMMs published until mid Mallah has reviewed the use of metallocyanates in making SMMs, and Cornia has reviewed the growing field of hybrid materials featuring SMMs. The review by Clérac, Coulon and Miyasaka covers the more recently discovered phenomena of single-chain magnets. Underlying all this chemistry is the physics; Curély and Barbara provide an article on the general theory of superexchange in molecular species. Probably the most disappointing aspect of research into SMMs has been the stubborn fact that the highest energy barrier to reorientation of magnetisation remained at around 60 K for a dozen years after the phenomenon was discovered. Recent developments have moved this barrier to 90 K, albeit for a mononuclear cobalt complex that cannot be isolated in the solid state[13]. The work by Koga and co-workers suggests a new route towards SMMs, involving photoactivated heterospin systems. The other route that is becoming popular is to incorporate lanthanides and other heavier metal ions in an attempt to increase the anisotropy of the system. While this could raise the energy barrier, a significant breakthrough is required before we can consider making SMMs that store magnetic information at room temperature. Regardless of whether information storage in molecules at applicable temperatures is possible, the quantum phenomena that have been discovered and investigated over the last dozen years are fascinating. It is also possible that these phenomena may offer an alternate route to applications. Manchester, February 2006 Richard Winpenny

11 Preface XI References 1. Christou, G (1989) Acc Chem Res 22: Boyd PDW, Li Q, Vincent JB, Folting K, Chang H, Streib W, Huffman JC, Christou G, Hendrickson DN (1988) J Am Chem Soc 110: Lis T (1980) Acta Cryst B 36: Weinland RF, Fischer G (1921) Z Anorg Allg Chem 120: Caneschi A, Gatteschi D, Laugier J, Rey P, Sessoli R, Zanchini C (1988) J Am Chem Soc 110: Caneschi A, Gatteschi D, Sessoli R, Barra AL, Brunel LC, Guillot M (1991) J Am Chem Soc 113: Sessoli R, Gatteschi D, Caneschi A, Novak MA (1993) Nature 365: Sessoli R, Tsai HL, Schake AR, Wang SY, Vincent JB, Folting K, Gatteschi D, Christou G, Hendrickson DN (1993) J Am Chem Soc 115: Thomas L, Lionti F, Ballou R, Gatteschi D, Sessoli R, Barbara B (1996) Nature 383: Friedman JR, Sarachik MP, Tejada J, Ziolo R (1996) Phys Rev Lett 76: Gatteschi D, Sessoli R, Cornia A (2004) Comp Coord Chem 7: Gatteschi D, Sessoli R (2003) Angew Chem Int Ed 42: Koga N, Karasawa S (2005) Bull Chem Soc Jpn 78:1384

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13 Contents Synthesis of 3d Metallic Single-Molecule Magnets G.Aromí E.K.Brechin... 1 Spectroscopy of Single-Molecule Magnets E.J.L.McInnes Synthesis of Single-Molecule Magnets Using Metallocyanates J.-N.Rebilly T.Mallah PreparationofNovelMaterialsUsingSMMs A. Cornia A. F. Costantino L. Zobbi A. Caneschi D. Gatteschi M.Mannini R.Sessoli Single-Chain Magnets: Theoretical Approach and Experimental Systems C.Coulon H.Miyasaka R.Clérac General Theory of Superexchange in Molecules J.Curély B.Barbara Author Index Volumes Subject Index

14 Contents of Volume 117 Magnetic Functions Beyond the Spin-Hamiltonian Volume Editor: D. Michael P. Mingos ISBN: X Magnetic Parameters and Magnetic Functions in Mononuclear Complexes Beyond the Spin-Hamiltonian Formalism R. Boča 1 Introduction 2 Energy Levels of Multiterm Systems 3 Modeling the Magnetic Parameters 4 Calculations of Energy Levels and Magnetic Parameters 5 Empirical Magnetic Parameters 6 Conclusions Appendix A Spectroscopic Constants, Coefficients, and Matrix Elements B Irreducible Tensors and Tensor Operators C Classification of Crystal-Field Terms and Multiplets D Calculated Energy Levels and Magnetic Parameters References