Dear Colleagues,

The synthesis and chemical study of polymetallic compounds has been a relevant topic in different areas of Inorganic and Organometallic Chemistry over the past decades, mainly as consequence of their potential application in homo- and heterogeneous catalysis, but also for the novel electronic or magnetic properties that these compounds can display. Polynuclear complexes containing two or more different paramagnetic ions are of high interest in molecular magnetism. Numerous Single Molecule Magnets (SMMs) and Single Chain Magnets (SCMs), and most of the 3D molecule-based magnets are heterometallic complexes. Of particular interest are the Metal–Organic Frameworks (MOFs) constructed from different metallic nodes. Various applications for MOFs have been envisioned: separation and storage of specific molecules, catalysis, multifunctional materials, etc. The close proximity of the metals in these systems lies at the heart of their enhanced properties, as it allows the metals to act through cooperative and synergistic pathways that are impossible for related mononuclear complexes. Typically, the approximation of the metals is achieved by the presence of direct metal-metal bonds or by using suitable bridging ligands, which can also provide additional stability to the system. In search of new properties and/or better catalytic activities, a natural extension of these works that gained tremendous interest recently is the preparation of heterometallic complexes bearing different metal atoms. There are several appealing reasons for the renewed interest in this area. Firstly, in nature, several natural enzymes are based on electron transfer steps taking place at different metal atoms held together by the enzyme backbone, and this has prompted interest in preparing molecular mimics capable of accomplishing similar processes. Secondly, the different electronic and coordinative preferences of two different metals can give rise to chemical properties and reactivity departing significantly from those of each isolated fragment. Thirdly, there is a fundamental interest in the study of new M-M′ bonding interactions, especially for multiply bonded systems. Finally, tandem processes might also benefit from the combined presence of two different metals in a complex, with each metal completing specifically one elementary transformation as part of a more complex process.

This Special Issue of Inorganics, entitled “Heterometallic Complexes”, will deal with the new synthetic methods developed for the preparation of heterometallic complexes, but also with aspects such as the collection of new structural information, the analysis of their electronic structure, and the bonding or the development of novel applications in catalysis and beyond.

Prof. Dr. Daniel García‐Vivó
Prof. Dr. Marius Andruh
Guest Editors

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• heterometallic compounds
• polynuclear compounds
• metal–metal bonding
• small molecule activation
• electronic structure
• molecular magnetism
• tandem catalysis