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Molecular Bridge Engineering for Tuning Quantum Electronic Transport and Anisotropy in Nanoporous Graphene

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AMER CHEMICAL SOC
DOI: 10.1021/jacs.3c00173

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Recent advances in surface-assisted synthesis have demonstrated the ability to create highly anisotropic nanoporous graphene structures by laterally coupling arrays of nanometer wide graphene nanoribbons. In this study, a new nanoporous graphene structure was synthesized in which the interribbon electronic coupling can be controlled by phenylene bridges. The versatility of this structure arises from the multiple configurations of phenylene cross-coupling and the twist angle, which can be altered by interaction with the substrate and other external stimuli.
Recent advances on surface-assisted synthesis have demonstrated that arrays of nanometer wide graphene nanoribbons can be laterally coupled with atomic precision to give rise to a highly anisotropic nanoporous graphene structure. Electronically, this graphene nanoarchitecture can be conceived as a set of weakly coupled semiconducting 1D nanochannels with electron propagation characterized by substantial interchannel quantum interferences. Here, we report the synthesis of a new nanoporous graphene structure where the interribbon electronic coupling can be controlled by the different degrees of freedom provided by phenylene bridges that couple the conducting channels. This versat i l i t y arises from the multiplicity of phenylene cross-coupling configurations, which provides a robust chemical knob, and from the interphenyl twist angle that acts as a fine-tunable knob. The twist angle is significa n t l y altered by the interaction with the substrate, as confirmed by a combined bond-resolved scanning tunneling microscopy (STM) and ab initio analysis, and should accordingly be addressable by other external stimuli. Electron propagation simulations demonstrate the capabi l i t y of either switching on/off or modulating the interribbon coupling by the corresponding use of the chemical or the conformational knob. Molecular bridges therefore emerge as efficient tools to engineer quantum transport and anisotropy in carbon-based 2D nanoarchitectures.

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