Ladder-type conjugated molecules as robust multi-state single-molecule switches

Abstract

•Synthesis of a methylthio-functionalized, ladder-type oligoaniline derivative •Excellent stability and high molecular conductance in oxidized and protonated states •Robust switching of single-molecule conductance among three different states Ladder-type molecular structures greatly enhance the chemical stability of oligoaniline derivatives and impart well-defined physical properties to multiple molecular charge states. In this work, we characterize the charge transport properties of a ladder-type cyclohexadiene-1,4-diimine derivative at various protonation, lithiation, and oxidation states using single-molecule techniques. Our results show that a ladder-type oligoaniline derivative serves as a robust and reversible molecular switch with over two orders of magnitude changes in molecular conductance when controlled using chemical or electrochemical stimuli. Experimental results are complemented by molecular modeling using density functional theory (DFT) and nonequilibrium Green’s function-DFT (NEGF-DFT) to elucidate charge transport mechanisms at different molecular states. Overall, this work provides new strategies for advancing the stability, programmability, and efficiency of molecular charge transport using ladder-type single-molecule switches. Ladder-type molecular structures greatly enhance the chemical stability of oligoaniline derivatives and impart well-defined physical properties to multiple molecular charge states. In this work, we characterize the charge transport properties of a ladder-type cyclohexadiene-1,4-diimine derivative at various protonation, lithiation, and oxidation states using single-molecule techniques. Our results show that a ladder-type oligoaniline derivative serves as a robust and reversible molecular switch with over two orders of magnitude changes in molecular conductance when controlled using chemical or electrochemical stimuli. Experimental results are complemented by molecular modeling using density functional theory (DFT) and nonequilibrium Green’s function-DFT (NEGF-DFT) to elucidate charge transport mechanisms at different molecular states. Overall, this work provides new strategies for advancing the stability, programmability, and efficiency of molecular charge transport using ladder-type single-molecule switches.