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首页> 外文期刊>Chemistry: A European journal >Ordered arrays of organometallic iridium complexes with long alkyl chains on graphite
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Ordered arrays of organometallic iridium complexes with long alkyl chains on graphite

机译：石墨上具有长烷基链的有机金属铱配合物的有序阵列

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摘要

Iridium(III) fac-tris(2-phenylpyridine) fac-[Ir(ppy)(3)] complexes equipped with long alkyl chains were prepared to examine their capability to form organized arrays on the surface of highly oriented pyrolytic graphite (HOPG). The molecules form lamellar arrays at the 1-phenyloctane/HOPG interface. From the analysis of the STM images, it was concluded that the molecules align with alkyl chains being interdigitated. Similar lamellar arrays were also obtained at the air/HOPG interface upon drop-casting of toluene solutions. The lamellar structure at the molecular level leads to rectangular two-dimensional crystalline domains a few hundred nanometers long (nanoslips). Infrared external reflection spectroscopy suggested that the adsorbed alkyl chains adopt the trans-zig-zag conformation in the nanoslip, although the orientations of the zigzag plane of the alkyl groups are mixed. Cyclic, voltammetry indicates fast electron transfer between the adsorbed molecules and the substrate and significant intermolecular electronic interactions. It was found that annealing at high temperatures is an effective method to prepare ordered assemblies more than a few micrometer scale (microslips). The orientations of the nanoslips prepared from the racemic mixture exhibited an apparent 12-fold symmetry, while its optically active enantiomer resulted in more irregular domains with a six-fold symmetry, implying an important role of chirality on packing at the molecular level and on the orientation of the domains at larger scales. When drop-cast from more concentrated solutions than a few hundreds of micromolar, multilayers were obtained, in which the alkyl chains in the molecules are more or less perpendicular to the surface. This structure can be transformed into the nanoslips upon standing.
机译：制备了具有长烷基链的铱（III）fac-三（2-苯基吡啶）fac- [Ir（ppy）（3）]配合物，以检查其在高度取向的热解石墨（HOPG）表面上形成有序阵列的能力。分子在1-苯基辛烷/ HOPG界面形成层状阵列。从STM图像的分析可以得出结论，分子与被叉指的烷基链对齐。在滴入甲苯溶液后，在空气/ HOPG界面处也获得了类似的层状阵列。在分子水平上的层状结构导致长为几百纳米长的矩形二维晶域（纳米晶）。红外外反射光谱表明，尽管烷基的锯齿形平面的方向混合，但吸附的烷基链在纳米滑片中采用了反之字形构象。循环伏安法表明吸附的分子与底物之间的快速电子转移以及明显的分子间电子相互作用。已经发现，高温退火是制备大于几微米规模（微片）的有序组件的有效方法。由外消旋混合物制备的纳米级玻片的取向表现出明显的12倍对称性，而其旋光对映异构体则导致具有6倍对称性的更多不规则结构域，这表明手性在分子水平和分子堆积方面起着重要作用。域的方向较大。当从比几百微摩尔更浓的溶液中滴铸时，获得了多层，其中分子中的烷基链或多或少地垂直于表面。站立时可以将这种结构转变成纳米片。

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