Dictating Packing and Interactions of Perylene Bisimides within Cyclophane Structures in the Solid State

Abstract

Crystal packing and chromophore communication are key parameters for the performance and functionality of many applications related to light‐energy harvesting and conversion. However, obtaining crystals of flexible and very soluble structures is troublesome. Nevertheless, a crystal structure of a highly flexible perylene‐3,4 : 9,10‐tetracarboxylic acid bisimide (PBI) cyclophane was obtained and analysed to compare the chromophore arrangement in the solid state with theconfiguration in solution as well as with calculated structures. The crystal structure exhibits an intra‐ and intermolecular slip‐stack arrangement of the heterochiral PBI units, forming a unique one‐dimensional π‐stacking supramolecular polymer‐like structure. These findings emphasize that the unique solid‐state arrangement of the chromophores cannot be easily predicted by elaborate studies in solution or by theoretical calculations. Furthermore, it features the importance of controlling the crystal packing to enable specific applications based on multiexciton generation processes where the spatial dependence and relative orientation of the chromophores are decisive parameters.

A Chirally Locked Bis-perylene Diimide Macrocycle: Consequences for Chiral Self-Assembly and Circularly Polarized Luminescence

“…Perylene diimides (PDIs) are a class of luminescent organic dyes and promising supramolecular building blocks for chiroptical materials. − Alongside excellent photophysical properties, PDIs that are functionalized at one or more of their bay positions (1,6,7,12) are chiral due to twisting of the aromatic perylene core, which generates M or P atropisomers (Figure a) . Core twisted PDIs may undergo self-assembly through π–π interactions, − which provides the potential to amplify the g lum of CPL due to excitonic coupling between the chiral chromophores. , However, CPL measurements on single crystals of PDI dyes are unprecedented.…”