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RESEARCH PRODUCT

Preface for the Forum on Molecular Magnetism: The Role of Inorganic Chemistry

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Molecular magnetism is a rapidly expanding field of research whose central theme is the design and study of magnetic molecules and materials with tunable properties. In the early stages of the field, which began to take shape in the 1980s, much of the effort was directed at the pursuit of molecule-based magnetic solids that order at high temperatures. These materials are basically of two types: those based on tetracyanoethylene (TCNE) and those based on cyanide. As the field rapidly evolved over the past two decades, exciting new challenges appeared on the horizon, including the use of building block approaches for the preparation of complex multifunctional magnetic materials, the fabrication of nanosized magnetic molecules and other nanostructures that exhibit quantum effects, and, the ultimate frontier, viz., the realization of practical applications. In all of these developments, inorganic chemistry, and, in particular, coordination chemistry, plays a principal role. The purpose of this Forum issue is to highlight recent progress and perspectives in this diverse field and to underscore the influence of inorganic chemistry on an important area of materials science. A common thread that runs throughout research in molecular magnetism of metal ions is the application of classical coordination chemistry concepts as mapped out 150 years ago by the father of modern coordination chemistry, Alfred Werner. Given that Prussian Blue, Fe4[Fe(CN)6]3 ·14H2O, the first coordination compound and first molecule-based magnetic solid, was discovered in 1704 by the Berlin artist Diesbach,3 it is remarkable that, some 300 years later, we are only beginning to realize the enormous potential of cyanide materials and other magnetic coordination compounds. Indeed, Andreas Ludi, who dubbed Prussian Blue “The Inorganic Evergreen” in an article published in Journal of Chemical Education in 1981, was more visionary than he could have realized when he wrote those words. It is a privilege to follow in the footsteps of Alfred Werner and many other luminaries in the field of coordination chemistry, who have made countless seminal contributions to magnetism in the areas of synthetic inorganic and bioinorganic chemistry, theory, and spectroscopy, essential tools for magnetochemists in the year 2009. Current trends in molecular magnetism revolve around two main classes of materials, viz., multifunctional magnetic materials and molecular nanomagnets. Multifunctional materials hold promise for the realization of technologically important properties previously thought to be possible only with atom-based inorganic solids (e.g., magnetic ordering combined with conductivity, superconductivity, or ferroelectricity). An extensive class of magnetic materials of this type falls into the category of switching magnetic materials. The * To whom correspondence should be addressed. E-mail: dunbar@ mail.chem.tamu.edu. † Universidad de Valencia. ‡ Texas AM Epstein, A. J.; Reiff, W. M. Mol. Cryst. Liq. Cryst. 1985, 120, 27. (b) Miller, J. S.; Calabrese, J. C.; Epstein, A. J.; Bigelow, R. W.; Zhang, J. H.; Reiff, W. M. J. Chem. Soc., Chem. Commun. 1986, 1026. (c) Miller, J. S.; Calabrese, J. C.; Rommelmann, H.; Chittipeddi, S. R.; Zhang, J. H.; Reiff, W. M.; Epstein, A. J. J. Am. Chem. Soc. 1987, 109, 769. (d) Chittipeddi, S.; Cromack, K. R.; Miller, J. S.; Epstein, A. J. Phys. ReV. Lett. 1987, 58, 2695. (e) Yee, G. T.; Miller, J. S. In MagnetismsMolecules to Materials; Miller, J. S., Drillon, M., Eds.; Wiley-VCH: Weinheim, Germany, 2004; Vol. 5, p 223. (f) Gama, V.; Duarte, M. T. In MagnetismsMolecules to Materials; Miller, J. S., Drillon, M., Eds.; Wiley-VCH: Weinheim, Germany, 2004; Vol. 5. (2) (a) Babel, D. Comments Inorg. Chem. 1986, 5. (b) Dunbar, K. R.; Heintz, R. A. Prog. Inorg. Chem. 1997, 45, 283. (c) Verdaguer, M.; Bleuzen, A.; Marvaud, A. V.; Vaissermann, J.; Seuleiman, M.; Desplanches, C.; Scuiller, A.; Train, C.; Garde, R.; Gelly, G.; Lomenech, C.; Rosenman, I.; Veillet, P.; Cartier, C.; Villain, F. Coord. Chem. ReV. 1999, 192, 1023. (d) Verdaguer, M.; Girolami, G. S. Magn.: Mol. Mater. V 2005, 283. (e) Rebilly, J. N.; Mallah, T. Struct. Bonding (Berlin) 2006, 122, 103. (f) Shatruk, M.; Avendano, C.; Dunbar, K. R. Prog. Inorg. Chem. 2009, 56, 155-334. (3) (a) Frisch, J. L. Miscellanea Berolinensia ad Incrementum Scientiarum 1710, 1, 377–378. (b) Woodward, J. Philos. Trans. 1724, 33, 15–17. (c) Brown, J. Philos. Trans. 1724, 33, 17–24. (4) Ludi, A. J. Chem. Educ. 1981, 58, 1013. Inorg. Chem. 2009, 48, 3293-3295