Bäumer Nils, Hu Peiqi, Naruse Miku, Ogi Soichiro, Hudson Zachary M, Yamaguchi Shigehiro
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Furo, Chikusa, Nagoya, 464-8601, Japan.
Department of Chemistry, The University of British Columbia, Vancouver, British Columbia, V6T 1Z1, Canada.
Angew Chem Int Ed Engl. 2025 Aug 18;64(34):e202509241. doi: 10.1002/anie.202509241. Epub 2025 Jun 30.
Thermally activated delayed fluorescence (TADF) offers great potential for application in light emitting devices and bioimaging. Supramolecular polymers can offer intriguing properties for the same applications, such as stimuli responsiveness and self-healing owing to their dynamic intermolecular interactions. However, merging the two has remained a formidable challenge, due to the nonplanar geometry of common TADF chromophores. Herein, we overcome this challenge by utilizing a less distorted multiple resonance TADF (MR-TADF) chromophore connected to a polymerization inducing building block. The obtained supramolecular synthon is capable of assembling in aliphatic solvents due to combined interchromophore interactions and hydrogen bonding. Within the supramolecular ensemble the long-lived photoluminescence properties of the chromophore are maintained. Further modification of the photoluminescence properties could be achieved by using different supramolecular modulators in a social self-sorting approach, allowing fine-tuning of the photoluminescence lifetime and bandwidth. Notably, the extent of intermolecular interactions can switch these assemblies from kinetically to thermodynamically controlled regimes. Finally, we employ this co-assembly strategy to move from organic to aqueous media highlighting the potential toward biological applications.
热激活延迟荧光（TADF）在发光器件和生物成像领域具有巨大的应用潜力。超分子聚合物由于其动态分子间相互作用，在相同应用中可展现出诸如刺激响应性和自愈性等有趣特性。然而，由于常见TADF发色团的非平面几何结构，将两者结合一直是一项艰巨的挑战。在此，我们通过利用连接到聚合诱导结构单元的扭曲程度较小的多重共振TADF（MR-TADF）发色团克服了这一挑战。由于发色团间相互作用和氢键的共同作用，所获得的超分子合成子能够在脂肪族溶剂中组装。在超分子聚集体中，发色团的长寿命光致发光特性得以保持。通过在协同自分类方法中使用不同的超分子调节剂，可以实现对光致发光特性的进一步修饰，从而实现对光致发光寿命和带宽的微调。值得注意的是，分子间相互作用的程度可将这些组装体从动力学控制状态转变为热力学控制状态。最后，我们采用这种共组装策略，从有机介质转向水性介质，凸显了其在生物应用方面的潜力。
