Unraveling the Configuration Modulation in Spiro‐based Through‐Space Charge Transfer Materials

Thermally activated delayed fluorescence (TADF) materials hold promise for optoelectronic applications. Among various design strategies, through‐space charge transfer (TSCT) systems offer the potential for enhanced performance. However, the relationship between molecular configuration and TSCT properties remains unclear compared to traditional through‐band charge transfer materials. In this study, we investigated the influence of spatial configuration on TSCT features and electronic properties of triplet excited states in these TSCT materials. By manipulating the spatial arrangement between donor and acceptor segments using different spiro skeletons, a series of TSCT materials (DMB2‐DMB5) was synthesized. Together with the parent molecule, DM‐B, these materials exhibited completely different TADF characteristics, demonstrating the impact of spatial arrangements on their optoelectronic properties. Thus, the external quantum efficiency of these materials ranged from as high as 28.0% (DMB2) to as low as 3.6% (DMB5) due to variations in their TADF characteristics. Our findings highlight the significance of spatial configuration, beyond distance alone, in influencing TSCT properties when donor and acceptor segments are sufficiently close. This insight provides valuable guidance for developing advanced TSCT materials and advancing TADF systems with improved performance and functionality.