Topologically Matching Supramolecular n/p-Heterojunction Architectures
Topologically Matching Supramolecular n/p-Heterojunction Architectures
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DOI：
10.1002/anie.200902551
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发表时间：
2009-01-01
影响因子：
16.6
通讯作者：
Matile, Stefan
中科院分区：
文献类型：
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作者：
Bhosale, Rajesh;Perez-Velasco, Alejandro;Matile, Stefan
在光合作用中，沿着复杂的氧化还原/能量梯度进行的定向能量、电子和空穴传输在光合作用中是必不可少的。[1]应用于分子光电子学，例如块状n/p异质结(BHJ)有机太阳能电池，[2，3]这些来自自然的经验[4]呼吁建立n-和p-半导体路径在分子水平上同轴排列的系统。这些超分子n/p异质结(SHJ)必须包含适当放置的不同颜色和不同氧化还原性质的生色团，以吸收尽可能多的光并迅速将生成的电子和空穴向相反方向移动。超分子化学方法似乎是创建这种具有定向多色反平行氧化还原梯度(OMARGs)的SHJ的完美方法。然而，尽管许多小组做出了努力，到目前为止，通往OMARG-SHJ的可靠的自下而上的路线还不存在。[5-22]我们已经考虑了沿着聚苯基(POP)支架的萘二亚胺(NDI)π堆叠的拉链组装，以构建应对这一挑战所需的表面结构。[20-22]在此，我们引入低聚苯乙炔(OPE)支架来探索拉链结构的拓扑匹配的重要性，并确定拉链组装与OMARG-SHJ的创建的兼容性。在拉链组装中，附着在刚性杆支架上的[20，21]NDI发色团逐级组装，沿着交错的刚性支架建立相互交错的π堆栈，分别作为空穴(h+)和电子(e±)的传输路径。π被选为拉链组装中的π堆栈是因为它们统一了有利的性能，例如1)所有颜色的可用性，2)随着带隙的增加而降低HOMO/LUMO水平(图1)，3)n-半导性，4)NDI酸性，5)平面性，6)全局结构保持，7)紧凑性(“原子效率”)，以及8)合成可访问性。然而，POP对于拉链组装不是完美的，因为它们的重复距离(约10)超过了面对面π堆栈(2约3.5；图2).[23]与POP相比，OPE对于π堆叠架构具有完美的重复(约7)。此外，Opes是可平面化的，[27，28]更好的和红移的荧光团，[17]更好的孔洞
Directional energy, electron, and hole transport along sophisticated redox/energy gradients to and from active site is essential in photosynthesis.[1] Applied to molecular optoelectronics, such as bulk n/p-heterojunction (BHJ) organic solar cells,[2, 3] these lessons from nature [4] call for systems in which n-and p-semiconducting pathways are aligned coaxially at the molecular level. These supramolecular n/p-heterojunctions (SHJs) will have to contain judiciously placed chromophores of different color and with different redox properties to absorb as much light as possible and rapidly move the generated electrons and holes in opposite directions. Supramolecular chemistry approaches appear to be perfect for creating such SHJs with oriented multicolored antiparallel redox gradients (OMARGs). However, reliable bottom-up routes toward OMARG-SHJs do not exist to date, despite efforts by many groups.[5–22] We have considered the zipper assembly of naphthalenediimide (NDI) π stacks along poligophenyl (POP) scaffolds to construct the surface architectures needed to tackle this challenge.[20–22] Herein, we introduce oligophenylethynyl (OPE) scaffolds to explore the importance of topological matching for zipper architectures and to determine the compatibility of zipper assembly with the creation of OMARG-SHJs. In zipper assembly,[20, 21] NDI chromophores attached to rigid-rod scaffolds are assembled step-by-step to build mutually interdigitating π stacks along interdigitating rigidrod scaffolds, which should serve as hole (h+) and electron (eÀ) transporting pathways, respectively. NDIs were selected as π stacks in zipper assembly because they unify favorable properties, such as 1) availability in all colors, 2) decreasing HOMO/LUMO levels with increasing bandgap (Figure 1), 3) n-semiconductivity, 4) π acidity, 5) planarity, 6) global structural preservation, 7) compactness (“atom efficiency”), and 8) synthetic accessibility.[19–26]POPs are however not perfect for zipper assembly because their repeat distance (about 10) exceeds the repeat of face-to-face π stacks (2 circa 3.5; Figure 2).[23] In contrast to POPs, OPEs have perfect repeats (circa 7) for π-stacking architectures. Moreover, OPEs are planarizable,[27, 28] better and red-shifted fluorophores,[17] better hole