Bondarenko Anna S, Patmanidis Ilias, Alessandri Riccardo, Souza Paulo C T, Jansen Thomas L C, de Vries Alex H, Marrink Siewert J, Knoester Jasper
University of Groningen, Zernike Institute for Advanced Materials Groningen The Netherlands
University of Groningen, Groningen Biomolecular Sciences and Biotechnology Institute Groningen The Netherlands.
Chem Sci. 2020 Oct 1;11(42):11514-11524. doi: 10.1039/d0sc03110k.
Supramolecular aggregates of synthetic dye molecules offer great perspectives to prepare biomimetic functional materials for light-harvesting and energy transport. The design is complicated by the fact that structure-property relationships are hard to establish, because the molecular packing results from a delicate balance of interactions and the excitonic properties that dictate the optics and excited state dynamics, in turn sensitively depend on this packing. Here we show how an iterative multiscale approach combining molecular dynamics and quantum mechanical exciton modeling can be used to obtain accurate insight into the packing of thousands of cyanine dye molecules in a complex double-walled tubular aggregate in close interaction with its solvent environment. Our approach allows us to answer open questions not only on the structure of these prototypical aggregates, but also about their molecular-scale structural and energetic heterogeneity, as well as on the microscopic origin of their photophysical properties. This opens the route to accurate predictions of energy transport and other functional properties.
合成染料分子的超分子聚集体为制备用于光捕获和能量传输的仿生功能材料提供了广阔前景。由于分子堆积是由相互作用的微妙平衡导致的，而决定光学和激发态动力学的激子性质又反过来敏感地依赖于这种堆积，因此很难建立结构-性质关系，这使得设计变得复杂。在这里，我们展示了如何使用一种结合分子动力学和量子力学激子建模的迭代多尺度方法，来准确洞察数千个菁染料分子在与溶剂环境紧密相互作用的复杂双壁管状聚集体中的堆积情况。我们的方法不仅使我们能够回答关于这些典型聚集体结构的开放性问题，还能回答关于它们分子尺度的结构和能量异质性，以及它们光物理性质的微观起源的问题。这为准确预测能量传输和其他功能性质开辟了道路。
