Controlling Through‐Space and Through‐Bond Exchange Pathways in Bis‐Cobaltocenes for Molecular Spintronics. Issue 6 (30th December 2019)

• Record Type: Journal Article
• Authors: Puhl, Sarah; Steenbock, Torben; Herrmann, Carmen; Heck, Jürgen
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 6(2020)
• Page Start: 2407
• Page End: 2413
• Publication Date: 2019-12-30
• Subjects: Density functional calculations -- magnetic properties -- metallocenes -- molecular spintronics -- pathways; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201911999
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Pinching molecules via chemical strain suggests intuitive consequences, such as compression at the pinched site and clothespin‐like opening of other parts of the structure. If this opening affects two spin centers, it should result in reduced communication between them. We show that for naphthalene‐bridged biscobaltocenes with competing through‐space and through‐bond pathways, the consequences of pinching are far less intuitive: despite the known dominance of through‐space interactions, the bridge plays a much larger role for exchange spin coupling than previously assumed. Based on a combination of chemical synthesis, structural, magnetic, and redox characterization, and a newly developed theoretical pathway analysis, we can suggest a comprehensive explanation for this non‐intuitive behavior. These results are of interest for molecular spintronics, as naphthalene‐linked cobaltocenes can form wires on surfaces for potential spin‐only information transfer. Abstract : Chemical pinching increases the distance between spin centers. This should result in reduced through‐space exchange spin coupling. In naphthalene‐bridged biscobaltocenes, the bridge plays a larger role than anticipated, with pinching leading to an increase of spin coupling. This is important for tuning interactions in spin wires for information transfer.