Understanding the electronic properties of self-assembled materials by a combination of theory and experiment

二酰亚胺(PBI)和相关分子，如二酰亚胺(NBI)，形成了一类令人着迷的化合物。当用适当的取代基进行官能化时，它们的溶液可以形成凝胶或被分解成无定形薄膜。由此产生的自组装材料可以作为光电导体，即使在空气中也具有非常长的载流子寿命，作为析氢光催化剂和电池电解液，以及对电化学还原或照明做出结构响应的材料。所有这些性质都源于它们的自组装倾向与其丰富的氧化还原和光化学特性之间的相互作用。尽管它们具有有趣的性质和实用意义，但自组装材料的电子性质还没有被很好地理解。甚至在MZ小组中，作为与格拉斯哥的Adams和Draper小组合作的一部分，我们已经对这种材料进行了广泛的研究，到目前为止，我们几乎只专注于预测它们的光学性质。

Perylene bisimides (PBIs, or perylene dimides, PDIs) and related molecules, such asnaphthalene bisimides (NBIs), form a fascinating class of compounds. Whenfunctionalised with suitable substituents solutions of them can form gels or be drieddown to amorphous thin films. The resulting self-assembled materials can act asphotoconductors, with very long charge carrier lifetimes, even in the presence of air,as hydrogen evolution photocatalysts, and battery electrolytes, as well as materialsthat structural respond to electrochemical reduction or illumination. All theseproperties arise from the interplay between their propensity to self-assemble andtheir rich redox and photochemistry.Despite their interesting properties and practical relevance, the electronic propertiesof the self-assembled materials are not very well understood. Even in the MZ group,where we have studied such materials extensively as part of a collaboration with theAdams and Draper groups in Glasgow, we focused till date nearly exclusively on predicting their optical properties.