Although most molecular electronic devices and materials consist of a backbone with a planar structure, twisted molecular wires with reduced inter-ring π-orbital overlap offer a unique opportunity for the modularized fabrication of molecular electronic devices. Herein we investigate the modularized tuning of the charge transport through the localized molecules by designing highly twisted molecules and investigating their single-molecule charge transport using the scanning tunneling microscopy break junction technique. We find that the anthracenediyl-core molecule with a 90° inter-ring twist angle shows an unexpectedly high conductance value, which is five times higher than that of the phenylene-core molecule with a similar configuration, whereas the conductance of the delocalized planar molecule with an anthracenediyl core or a phenylene core is almost the same. Theoretical calculations revealed that highly twisted angles result in weak interactions between molecular building blocks, for which molecule orbitals are separated into localized blocks, which offers the chance for the modularized tuning of every single block. Our findings offer a new strategy for the design of future molecular devices with a localized electronic structure.

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