Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
J Am Chem Soc. 2013 Aug 14;135(32):12082-90. doi: 10.1021/ja405776a. Epub 2013 Aug 1.
We report a synthetic method to build oriented architectures with three coaxial π-stacks directly on solid surfaces. The approach operates with orthogonal dynamic bonds, disulfides and hydrazones, self-organizing surface-initiated polymerization (SOSIP), and templated stack-exchange (TSE). Compatibility with naphthalenediimides, perylenediimides, squaraines, fullerenes, oligothiophenes, and triphenylamine is confirmed. Compared to photosystems composed of two coaxial channels, the installation of a third channel increases photocurrent generation up to 10 times. Limitations concern giant stack exchangers that fail to enter SOSIP architectures (e.g., phthalocyanines surrounded by three fullerenes), and planar triads that can give folded or interdigitated charge-transfer architectures rather than three coaxial channels. The reported triple-channel surface architectures are as sophisticated as it gets today, the directionality of their construction promises general access to multichannel architectures with multicomponent gradients in each individual channel. The reported approach will allow us to systematically unravel the ultrafast photophysics of molecular dyads and triads in surface architectures, and might become useful to develop conceptually innovative optoelectronic devices.
我们报告了一种在固体表面上直接构建具有三个同轴π堆叠的取向结构的合成方法。该方法采用正交动态键（二硫键和腙键）、表面引发聚合（SOSIP）和模板堆叠交换（TSE）。该方法与萘二酰亚胺、苝二酰亚胺、方酸、富勒烯、寡聚噻吩和三苯胺兼容。与由两个同轴通道组成的光系统相比，安装第三个通道可将光电流生成提高 10 倍。限制因素包括无法进入 SOSIP 结构的巨型堆叠交换器（例如，被三个富勒烯包围的酞菁），以及可能产生折叠或互穿插的电荷转移结构而不是三个同轴通道的平面三联体。所报道的三通道表面结构是目前为止最复杂的，其构建的方向性有望普遍适用于每个通道都具有多组分梯度的多通道结构。所报道的方法将使我们能够系统地揭示表面结构中分子偶联物和三联体的超快光物理，并且可能有助于开发概念创新的光电设备。
