Controllable assembly of organic semiconductors has opened an avenue for an in-depth perception of their structure–property relationships; however, a detailed investigation of their molecular controllability remains challenging. Discerning the assembly of organic semiconductors could enable the attainment of a significant improvement of performance. Here, we report the fabrication of efficient nonfullerene organic solar cells (OSCs) based on two isomeric perylene diimide (PDI)-fused corannulene acceptors, namely, corannurylene pentapetalae (CRP). A single-crystal analysis demonstrated that differentially symmetric isomers such as CRP-1 and CRP-2 display various assembly framework structures. Both isomeric CRP acceptor-based solar cells showed excellent power conversion efficiencies matching a medium bandgap polymer donor (P3TEA). Compared with CRP-2, a high symmetry-induced orderly assembly endowed CRP-1 with a higher efficiency of 11.2%, which is the maximum performance of PDI-based OSCs reported to date. This study sheds light on designing high-performance organic semiconductors allowing for symmetric orderly assembly.

有机半导体的可控组装为深入了解其结构-性质关系开辟了一条途径。然而，对其分子可控性的详细研究仍具有挑战性。辨别有机半导体的组装可以实现性能的显着改善。在这里，我们报告基于两个异构per二酰亚胺（PDI）融合的并茂碳烯受体，即，并茂碳戊二烯（CRP）的高效非富勒烯有机太阳能电池（OSC）的制造。单晶分析表明，差异对称异构体（例如CRP-1和CRP-2）显示出各种组装框架结构。两种基于CRP受体的异构体太阳能电池均具有出色的功率转换效率，与中等带隙聚合物供体（P3TEA）相匹配。与CRP-2相比，高对称性诱导的有序组装赋予CRP-1更高的效率11.2％，这是迄今为止报道的基于PDI的OSC的最大性能。这项研究为设计允许对称有序组装的高性能有机半导体提供了启示。