Crystal Engineering of 1D Exciton Systems Composed of Single‐ and Double‐Stranded Perylene Bisimide J‐Aggregates
Crystal Engineering of 1D Exciton Systems Composed of Single‐ and Double‐Stranded Perylene Bisimide J‐Aggregates
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DOI：
10.1002/adom.202000926
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发表时间：
2020-06
影响因子：
9
通讯作者：
M. Stolte;R. Hecht;Zengqi Xie;Linlin Liu;Christina Kaufmann;Astrid Kudzus;D. Schmidt;F. Würthner
中科院分区：
文献类型：
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作者：
M. Stolte;R. Hecht;Zengqi Xie;Linlin Liu;Christina Kaufmann;Astrid Kudzus;D. Schmidt;F. Würthner
通过真空升华生长三种在湾区四苯氧基取代的二萘嵌苯双酰亚胺染料的单晶。X射线分析揭示了这些高度扭曲的苝双酰亚胺（PBI）在固态下通过酰亚胺-酰亚胺氢键结合成氢键PBI链的自组装。晶体学见解揭示了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，虽然空间要求较低的甲基和异丙基取代基提供互补的P和M对映异构体的双链PBI链，但对于空间要求较高的邻苯基取代基观察到纯手性PBI的单个氢键键合链。这些PBIs的微晶和薄膜的吸收和荧光特性的调查允许这些激子系统的明确的解释。因此，双链晶体的J-聚集体表现出比单链晶体大得多的（负）激子耦合，相反，单链晶体具有更高的固态荧光量子产率。
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.