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首页> 外文期刊>Chemistry: A European journal >Disulfide- and thiol-incorporating copper catenanes: synthesis, deposition onto gold, and surface studies
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Disulfide- and thiol-incorporating copper catenanes: synthesis, deposition onto gold, and surface studies

机译：结合有二硫键和硫醇键的铜链烷烃：合成，金沉积和表面研究

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Two new copper-complexed [2]catenanes have been prepared, both of which consist of two different interlocking rings. In both cases, one of the rings incorporates a disulfide bridge. The other ring contains either a single chelate (phen = 1,10-phenanthroline, a bidentage ligand) or two different chelates (phen and terpy, 2,2',6',2"-terpyridine, a tridentate chelate). Deposition of these two complexes on a gold electrode surface was carried out by standard procedures, leading to reductive cleavage of the S-S bridge. The adsorbed species can be viewed as [2]catenanes for which the gold atoms of the electrode surface are an integral fragment of one of the two rings. They yield clear electrochemical responses, but no motion is observed for the catenane incorporating a phen unit and a terpy fragment in one of the two rings, regardless of the metal oxidation state. This is at odds with the behavior of the parent compound in solution, which undergoes ring-gliding motions upon electrochemical reduction or oxidation of the copper center. Near-field microscopy was used to study the deposited layers (STM and AFM). STM images suggest that the molecules do not tend to order at long range on the surface. Polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS) led to promising results: the two catenanes deposited are likely to be oriented perpendicular to the gold surface.
机译：已经制备了两种新的铜络合的[2] catenanes，它们都由两个不同的互锁环组成。在两种情况下，一个环都带有二硫键。另一个环含有一个螯合物（phen = 1,10-菲咯啉，二齿配体）或两个不同的螯合物（phen and terpy，2,2'，6'，2“ -terpyridine，一种三齿螯合物）。在金电极表面上的这两个络合物是通过标准程序进行的，导致SS桥的还原裂解，被吸附的物质可视为[2]邻苯二酚，其中电极表面的金原子是一个完整的碎片。它们产生清晰的电化学反应，但未观察到在两个环之一中并入phen单元和三联片段的连环烷的运动，而与金属的氧化态无关，这与环的行为不符。溶液中的母体化合物，在电化学还原或铜中心氧化后会经历滑环运动，近场显微镜用于研究沉积层（STM和AFM），STM图像表明分子在12时不趋于有序表面上的远射。偏振调制红外反射吸收光谱法（PM-IRRAS）产生了可喜的结果：沉积的两个链烷很可能垂直于金表面取向。

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