Tuning Optical Properties by Controlled Aggregation: Electroluminescence Assisted by Thermally‐Activated Delayed Fluorescence from Thin Films of Crystalline Chromophores

Several photophysical properties of chromophores depend crucially on intermolecular interactions. Thermally‐activated delayed fluorescence (TADF) is often influenced by close packing of the chromophore assembly. In this context, the metal‐organic framework (MOF) approach has several advantages: it can be used to steer aggregation such that the orientation within aggregated structures can be predicted using rational approaches. We demonstrate this design concept for a DPA‐TPE (diphenylamine‐tetraphenylethylene) chromophore, which is non‐emissive in its solvated state due to vibrational quenching. Turning this DPA‐TPE into a ditopic linker allows to grow oriented MOF thin films exhibiting pronounced green electroluminescence with low onset voltages. Measurements at different temperatures clearly demonstrate the presence of TADF. Finally, we show that the layer‐by‐layer process used for MOF thin film deposition allowed to integrate the TADF‐DPA‐TPE in a functioning LED device.