A new thermally activated delayed fluorescence (TADF)‐displaying macrocyclic compound m‐1 comprising of two electron‐donors (N,N’‐diphenyl‐m‐phenylenediamine) and two electron‐acceptors (dibenzo[a,j]phenazine) has been synthesized. The macrocycle developed herein is regarded as a regioisomer of the previously reported TADF macrocycle p‐1, which has two N,N’‐diphenyl‐p‐phenylenediamines as the donors. To understand the influence of the topology of the phenylenediamine donors on physicochemical properties of TADF‐active macrocycles, herein the molecular structure in the single crystals, photophysical properties, electrochemical behavior, and TADF properties of m‐1 have been investigated compared with those of p‐1. The substitution of p‐phenylene donor with m‐phenylene donor led to distinct positive solvatoluminochromism over the full visible‐color range, unique oxidative electropolymerization, and slightly lower contribution of TADF, due to the lower CT character in the excited states.

中文翻译：

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揭示苯二胺单元对供体-受体-供体-受体热激活延迟荧光大环化合物理化性质的拓扑影响。

一个新的热活化延迟荧光（TADF）-displaying大环化合物M-1包括两个电子给体（的N，N'-二苯基-米苯二胺）和两个电子受体（二苯并[一，J ]吩嗪）一直合成的。本文所开发的大环被认为是以前报道TADF大环化合物的区域异构体P-1 ，其具有两个N， N'-二苯基对-苯二胺作为供体。为了了解苯二胺供体的拓扑结构对TADF活性大环的理化性质的影响，本文对m-1的单晶分子结构，光物理性质，电化学行为和TADF性质进行了研究（与p相比）。‐1。的取代对-亚苯基供体与米导致在整个可见色彩范围不同的正solvatoluminochromism，独特的氧化电聚合，和TADF稍低的贡献，由于在激发态下CT字符亚苯基供体。