Tandem Four‐Component Reaction to Access Fused Polycycles Exhibiting Aggregation‐Enhanced Through‐Space Charge Transfer Emission

Rapid construction of new fluorescence emitters is essential in advancing synthetic luminescent materials. This study illustrated a piperidine‐promoted reaction of chiral dialdehyde with benzoylacetonitrile and malonitrile, leading to the formation of the 6/6/7 fused cyclic product in good yield. The proposed reaction mechanism involves a dual condensation/cyclization process, achieving the formation of up to six bonds for fused polycycles. The single crystal structure analysis revealed that the fused cyclic skeleton contains face‐to‐face naphthyl and cyanoalkenyl motifs, which act as the electronic donor and acceptor, respectively, potentially resulting in through‐space charge transfer (TSCT) emission. While the TSCT emissions were weak in solution, a notable increase in luminescence intensity was observed upon aggregation, indicating bright fluorescent light. A series of theoretical analyses further supported the possibility of spatial electronic communication based on frontier molecular orbitals, the distance of charge transfer, and reduced density gradient analysis. This work not only provides guidance for the one‐step synthesis of complex polycycles, but also offers valuable insights into the design of aggregation‐enhanced TSCT emission materials. A set of fused polycyclic compounds were synthesized efficiently through tandem four‐component reactions that incorporated a chiral binaphthyl‐based dicarbaldehyde, malonitrile and two carbonyl acetonitriles. Notably, Aggregation‐enhanced through‐space charge transfer emission could be observed based on the polycyclic spacer. Theoretical analyses further supported the possibility of spatial electronic communication.