A Redox‐active Cyclometalated Platinum Ring Enables Synthetic Post‐processing of a [2]Rotaxane

Abstract Post‐synthetic modification of mechanically interlocked molecules (MIMs) is an attractive avenue to add complexity to already intricate systems. This remains an important, challenging topic that is under‐developed. In this paper, we report the synthesis and characterization of a [2]rotaxane molecule featuring a ring appended to an emissive cyclometalated Pt II unit. Modulation of the oxidation state at the metal center can transform the interlocked molecule into a new Pt IV [2]rotaxane or a Pt III [3]rotaxane held together by an intermetallic Pt−Pt bond – a first of its kind. These molecules display distinct structural and photophysical properties, as well as shuttling dynamics. This approach for post‐synthetic modification could be used to construct more complex MIMs and inorganic supramolecular assemblies with redox properties.