Supramolecular light-absorbing nanostructures are useful building blocks for the design of next-generation artificial photosynthetic systems. Development of such systems requires a detailed understanding of how molecular packing influences the material's optoelectronic properties. We describe a series of crystalline supramolecular nanostructures in which the substituents on their monomeric units strongly affect morphology, ordering kinetics, and exciton behavior. By designing constitutionally isomeric perylene monoimide (PMI) amphiphiles, we studied the effect of side chain sterics on nanostructure crystallization. Molecules with short amine-linked alkyl tails rapidly crystallize upon dissolution in water, whereas bulkier tails require the addition of salt to screen electrostatic repulsion and annealing to drive crystallization. A PMI monomer bearing a 3-pentylamine tail was found to possess a unique structure that results in strongly red-shifted absorbance, indicative of charge-transfer exciton formation. This particular supramolecular structure was found to have an enhanced ability to photosensitize a thiomolybdate catalyst ((NH₄)₂Mo₃S₁₃) to generate hydrogen gas.

超分子光吸收纳米结构是设计下一代人工光合作用系统的有用构建基块。这种系统的开发需要对分子堆积如何影响材料的光电性能的详细了解。我们描述了一系列的结晶超分子纳米结构，其中其单体单元上的取代基强烈影响形态，有序动力学和激子行为。通过设计组成异构的per单酰亚胺（PMI）两亲物，我们研究了侧链空间位阻对纳米结构结晶的影响。具有短的胺连接的烷基尾巴的分子在溶解于水中后会迅速结晶，而体积较大的尾巴则需要添加盐以筛选静电排斥力并退火以驱动结晶。发现带有3-戊基胺尾的PMI单体具有独特的结构，该结构导致吸光度强烈红移，表明电荷转移激子的形成。发现该特定的超分子结构具有增强的光敏能力，使硫代钼酸盐催化剂（（NH₄）₂ Mo ₃ S ₁₃）产生氢气。