Metal-to-Metal Distance Modulation by Ligand Design: A Case Study of Structure-Property Correlation in Planar Chiral Cyclophanyl Metal Complexes.

Multinuclear metal complexes have seen tremendous progress in synthetic advances, their versatile structural features, and emerging applications. Here, we conceptualize Metal-to-Metal distance modulation in cyclophanyl metal complexes by bridging ligand design employing the co-facially stacked cyclophanyl-derived pseudo-geminal, -ortho, -meta, and -para constitutional isomers grafted with N-, O-, and P- containing chelates that allow the installation of diverse (hetero)metallic moieties in a distance-defined and spatially-oriented relation to one another. Metal-to-Metal distance modulation and innate transannular "through-space" π-π electronic interactions via the co-facially stacked benzene rings in cyclophanyl-derived complexes as well as their specific stereochemical structural features (element of planar chirality) are crucial factors that contribute to the tuning of structure-property relationships, which stand at the very center from the perspective of cooperative effects in catalysis as well as emerging material applications.