The charge‐transfer (CT) interactions between organic compounds are reflected in the (opto)electronic properties. Determining and visualizing crystal structures of CT complexes are essential for the design of functional materials with desirable properties. Complexes of pyranine (PYR), methyl viologen (MV), and their derivatives are the most studied water‐based CT complexes. Nevertheless, very few crystal structures of CT complexes have been reported so far. In this study, the structures of two PYRs‐MVs CT crystals and a map of the noncovalent interactions using 3D electron diffraction (3DED) are reported. Physical properties, e.g., band structure, conductivity, and electronic spectra of the CT complexes and their crystals are investigated and compared with a range of methods, including solid and liquid state spectroscopies and highly accurate quantum chemical calculations based on density functional theory (DFT). The combination of 3DED, spectroscopy, and DFT calculation can provide important insight into the structure‐property relationship of crystalline CT materials, especially for submicrometer‐sized crystals.

中文翻译：

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从头算确定的结构可视化亚微米尺寸电荷转移晶体的非共价相互作用和性质预测

有机化合物之间的电荷转移（CT）相互作用反映在（光）电子特性中。确定和可视化 CT 复合物的晶体结构对于设计具有所需性能的功能材料至关重要。吡喃 (PYR)、甲基紫精 (MV) 及其衍生物的配合物是研究最多的水基 CT 配合物。然而，迄今为止，CT复合物的晶体结构报道还很少。在这项研究中，报告了两种 PYRs-MVs CT 晶体的结构以及使用 3D 电子衍射 (3DED) 的非共价相互作用图。研究了 CT 配合物及其晶体的物理性质，例如能带结构、电导率和电子光谱，并与一系列方法进行比较，包括固态和液态光谱以及基于密度泛函理论 (DFT) 的高精度量子化学计算。 3DED、光谱学和 DFT 计算的结合可以为晶体 CT 材料的结构-性能关系提供重要的见解，特别是对于亚微米尺寸的晶体。