Synthetic Methodology for Structurally Defined and Insulated Molecular Wires Bearing Non‐centrosymmetric Conjugated Axle Components via Iterative Intramolecular Slippage

Insulated molecular wires (IMWs) bearing non‐centrosymmetric conjugated axle components were precisely synthesized via iterative cross‐coupling reactions in organic solvents and subsequent intramolecular slippage transformation in aqueous solvents. This programmable synthetic procedure selectively afforded both insulated and uninsulated molecular wires bearing oligo(phenylene ethynylene) and permethylated α‐cyclodextrins with well‐defined conjugation lengths and supramolecular structures. High selectivity of this method was confirmed by NMR and mass spectroscopic analyses. The resultant IMWs exhibited distinct optical properties because of different conjugation lengths and insulated structures. This synthetic strategy for structurally defined IMWs bearing non‐centrosymmetric conjugated axle components could provide a platform for obtaining diverse functionalized materials useful in the fields of non‐centrosymmetric molecular machines and molecular electronics.