Single crystals of three at bay area tetraphenoxy‐substituted perylene bisimide dyes are grown by vacuum sublimation. X‐ray analysis reveals the self‐assembly of these highly twisted perylene bisimides (PBIs) in the solid state via imide–imide hydrogen bonding into hydrogen‐bonded PBI chains. The crystallographic insights disclose that the conformation and sterical congestion imparted by the phenoxy substituents can be controlled by ortho‐substituents. Accordingly, whilst sterically less demanding methyl and isopropyl substituents afford double‐stranded PBI chains of complementary P and M atropo‐enantiomers, single hydrogen‐bonded chains of homochiral PBIs are observed for the sterically more demanding ortho‐phenyl substituents. Investigation of the absorption and fluorescence properties of microcrystals and thin films of these PBIs allow for an unambiguous interpretation of these exciton systems. Thus, the J‐aggregates of the double‐stranded crystals exhibit a much larger (negative) exciton coupling than the single‐stranded one, which in contrast has the higher solid‐state fluorescence quantum yield.

中文翻译：

---

由单链和双链Per双酰亚胺J-骨料构成的一维激子系统的晶体工程

通过真空升华，可在三倍于四苯氧基取代的bi双酰亚胺染料的湾区形成三个单晶。X射线分析揭示了这些高度扭曲的per双酰亚胺（PBI）在固态下通过酰亚胺-酰亚胺氢键结合成氢键PBI链而自组装。晶体学的见解表明，苯氧基取代基赋予的构象和空间拥挤可以通过邻位取代基控制。因此，尽管空间上对甲基和异丙基取代基的需求较少，但它们提供了互补的P和M阻转异构体对映体的双链PBI链，但对于空间上要求较高的邻位，则观察到同手性PBI的单氢键结合链-苯基取代基。对这些PBI的微晶和薄膜的吸收和荧光性质的研究可以对这些激子系统进行明确的解释。因此，双链晶体的J聚集体表现出比单链晶体更大的（负）激子耦合，而单链晶体的J聚集体具有更高的固态荧光量子产率。