Dissymmetry in paddlewheel chemistry

• Published in: Coordination chemistry reviews Vol. 544; p. 216979
• Main Authors: Coloma, Isabel, Cortijo, Miguel
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.12.2025
• Subjects: Chiral Clusters; Extended Metal Atom Chains (EMACs); Lantern structure; Metal-Metal Bonds; Paddlewheel structure; Extended Metal Atom Chains (EMACs); Paddlewheel structure; Chiral Clusters; Metal-Metal Bonds; Lantern structure
• ISSN: 0010-8545
• DOI: 10.1016/j.ccr.2025.216979

The paddlewheel structure is a robust and tunable motif profoundly explored in coordination chemistry since it leads to species with interesting fundamental and applied properties such as metal-metal bonding, electrochemistry, magnetism, nanoscience, biomedicine, and catalysis. Chirality can be introduced in such structural motifs by different means, being the simplest and most studied, employing enantiopure ligands with asymmetric carbon atoms. Most of the related reported literature is focused on the study of discrete homoleptic dirhodium complexes with chiral ligands and their fruitful application in asymmetric catalysis. This review does not intend to deepen into this subject since there are some relatively recent revision articles dealing with it. In turn, we aim to show in addition other alternatives that afford chiral paddlewheel structures. These design possibilities have been the subject of a smaller number of studies, however, they offer potential novel applications not only in catalysis, but also in other areas. In the first place, the development of systems with different types of chirality, beyond those containing only asymmetric carbon atoms is discussed, focusing also on chiral-at-metal clusters. This review deals with the synthesis and chiral resolution of these complexes showing the different examples of chiral binuclear and polynuclear complexes. In addition, these building blocks have been employed to study the assembly, using appropriate connectors, into discrete entities or coordination polymers. Finally, the spectroscopic properties measured with polarized radiation of enantiopure complexes and the most relevant applications, providing novel perspectives for future investigations, are discussed in the subsequent sections. •Different design possibilities to afford chiral paddlewheel structures.•Not limited to the most studied examples, i.e., homoleptic dirhodium compounds.•Binuclear and polynuclear complexes.•With point, helical or axial chirality.•Applications in catalysis, enantiodifferentiation, nanoscience and biomedicine. [Display omitted]