Heterometallic Mixed 3d-4f Metallacrowns: Structural Versatility, Luminescence, and Molecular Magnetism

Abstract

The synthesis of metal-containing coordination complexes has relevance in a number of applications, including catalysis, gas separations and storage, data storage, contrast agents, and drug delivery. As such, methods towards the a priori design of these materials are of great importance. Unlike organic synthesis, which is governed by well-known and understood reaction mechanisms, inorganic synthesis is dominated by labile metal-ligand dative bonds, whose reversibility in solution can lead to unanticipated molecules. However, the metallamacrocycles known as metallacrowns (MCs) provide the opportunity to investigate controllable inorganic syntheses, which can lead to systematic alterations of these molecules. Thus, entire classes of inorganic molecules may be designed with specific properties. In this review, 3d-4f metallacrowns will be examined, with emphasis on (1) synthetic and design aspects; (2) luminescence properties; and (3) magnetic behavior.

GRAPHICAL ABSTRACT

• coordination chemistry
• lanthanides
• luminescence
• magnetism
• metallacrowns
• transition metals

ACKNOWLEDGEMENTS

We appreciate the useful experimental and theoretical contributions of numerous colleagues, including Talal Mallah and Victoria Campbell (University of Paris-Sud), Stephane Petoud and Svetlana Eliseeva (Centre de Biophysique Molećulaire, Orleáns), and Aniruddha Deb and Jim Penner-Hahn (University of Michigan).