Methyldisulfide groups enable the direct connection of air-stable metal bis(terpyridine) complexes to gold surfaces
Methyldisulfide groups enable the direct connection of air-stable metal bis(terpyridine) complexes to gold surfaces
复制标题
甲基二硫基团能够将空气稳定的金属双（三联吡啶）配合物直接连接到金表面
DOI：
10.1039/d3dt00955f
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发表时间：
2023
影响因子：
4
通讯作者：
Inkpen, Michael S.
中科院分区：
文献类型：
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作者：
Trang, Christina D.;Saal, Thomas;Inkpen, Michael S.
我们表明，包含直接连接的甲基二硫基（tpySSMe）的新型三联吡啶配体可用于制备模块化系列金属双（terpyidine）配合物[M（tpySSMe）2]（PF 6）2（M = Fe、Co、Zn），适用于金属表面的功能化。关键的是，我们发现这些配合物在溶液中空气稳定>7 d，与它们的巯基取代的类似物[M（tpySH）2]（PF 6）2（M = Fe，Co）形成鲜明对比，后者在<1 d内分解。虽然CoSH以前曾被用于几个重要的研究，我们明确详细介绍其合成和表征在这里的第一次。随后，我们探测[M（tpySSMe）2]（PF6）2在溶液中的电化学性质，表明与二硫键还原相关的（电）化学反应显着增加伏安响应的复杂性。在初步的表面伏安法研究中，我们证实，CoSS和FeSS形成溶液稳定的自组装单分子膜（SAMs）的金与可比的电化学性能从CoSH形成的。总之，这项工作提供了一个强大的基础，为未来的研究这类突出的复合物作为自组装膜或单分子连接的氧化还原活性成分。
We show that a new terpyridine ligand comprising a directly-connected methyldisulfide group (tpySSMe) can be used to prepare a modular series of metal bis(terpyidine) complexes, [M(tpySSMe)2](PF6)2 (M = Fe, Co, Zn), suitable for the functionalization of metal surfaces. Critically, we find these complexes are air-stable in solution for >7 d, in stark contrast to their thiol-substituted analogues, [M(tpySH)2](PF6)2 (M = Fe, Co), which decompose in <1 d. While CoSH has previously been utilized in several important studies, we explicitly detail its synthesis and characterization here for the first time. We subsequently probe the electrochemical properties of [M(tpySSMe)2](PF6)2 in solution, showing that the (electro)chemical reactions associated with disulfide reduction significantly increase the complexity of the voltammetric response. In preliminary surface voltammetry studies, we confirm that CoSS and FeSS form solution-stable self-assembled monolayers (SAMs) on gold with comparable electrochemical properties to those formed from CoSH. Taken together, this work provides a robust foundation for future studies of this prominent class of complexes as redox-active components of SAMs or single-molecule junctions.