Optimizing Single-Molecule Conductivity of Conjugated Organic Oligomers with Carbodithioate Linkers

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• 作者：Yangjun Xing ; Tae-Hong Park ; Ravindra Venkatramani ; Shahar Keinan ; David N. Beratan ; Michael J. Therien ; Eric Borguet
• 刊名：Journal of the American Chemical Society
• 出版年：2010
• 出版时间：June 16, 2010
• 年：2010
• 卷：132
• 期：23
• 页码：7946-7956
• 全文大小：338K
• 年卷期：v.132,no.23(June 16, 2010)
• ISSN：1520-5126

文摘

In molecular electronics, the linker group, which attaches the functional molecular core to the electrode, plays a crucial role in determining the overall conductivity of the molecular junction. While much focus has been placed on optimizing molecular core conductivity, there have been relatively few attempts at designing optimal linker groups to metallic or semiconducting electrodes. The vast majority of molecular electronic studies use thiol linker groups; work probing alternative amine linker systems has only recently been explored. Here, we probe single-molecule conductances in phenylene−ethynylene molecules terminated with thiol and carbodithioate linkers, experimentally using STM break-junction methods and theoretically using a nonequilibrium Green’s function approach. Experimental studies demonstrate that the carbodithioate linker augments electronic coupling to the metal electrode and lowers the effective barrier for charge transport relative to the conventional thiol linker, thus enhancing the conductance of the linker−phenylene−ethynylene−linker unit; these data underscore that phenylene−ethynylene-based structures are more highly conductive than originally appreciated in molecular electronics applications. The theoretical analysis shows that the nature of sulfur hybridization in these species is responsible for the order-of-magnitude increased conductance in carbodithioate-terminated systems relative to identical conjugated structures that feature classic thiol linkers, independent of the mechanism of charge transport. Interestingly, in these systems, the tunneling current is not dominated by the frontier molecular orbitals. While barriers <k_BT are expected to produce low β values, we show that the competition between tunneling and resonant transport processes allows barriers k_BT to produce the low β values seen in our experiments. Taken together, these experimental and theoretical studies indicate a promising role for carbodithioate-based connectivity in molecular-scale electronics applications involving metallic and semiconducting electrodes.