Park Gyurim, Jeong Dong Yeon, Yu Seung Yeon, Park Jong Jin, Kim Jong H, Yang Hoichang, You Youngmin
Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul, 03722, Republic of Korea.
Division of Chemical Engineering and Materials Science, Ewha Womans University, Seoul, 03760, Republic of Korea.
Angew Chem Int Ed Engl. 2023 Oct 9;62(41):e202309762. doi: 10.1002/anie.202309762. Epub 2023 Sep 4.
In the dynamic domain of chiroptical technologies, it is imperative to engineer emitters endowed with circularly polarized luminescence (CPL) properties. This research demonstrates an advancement by employing a combined top-down and bottom-up strategy for the simultaneous amplification of photoluminescence quantum yield (Φ) and the luminescence dissymmetry factor (g ). Square-planar Pt(II) complexes form helical assemblies, driven by torsional strain induced by bis(nonyl) chains. Integration of chiral anions leads these assemblies to prefer distinct helical sense. This arrangement activates the metal-metal-to-ligand charge transfer (MMLCT) transition that is CPL-active, with Φ and |g | observing an upswing contingent on the charge number and aryl substituents in chiral anions. Utilizing the soft-lithographic micromolding in capillaries technique, we could fabricate exquisitely-ordered, one-dimensional co-assemblies to achieve the metrics to Φ of 0.32 and |g | of 0.13. Finally, our spectroscopic research elucidates the underlying mechanism for the dual amplification, making a significant stride in the advancement of CPL-active emitters.
在旋光技术这个充满活力的领域，设计具有圆偏振发光（CPL）特性的发光体至关重要。本研究展示了一种进步，即采用自上而下和自下而上相结合的策略，同时提高光致发光量子产率（Φ）和发光不对称因子（g）。平面正方形Pt（II）配合物形成螺旋组装体，由双（壬基）链诱导的扭转应变驱动。手性阴离子的整合使这些组装体倾向于不同的螺旋方向。这种排列激活了具有CPL活性的金属-金属-配体电荷转移（MMLCT）跃迁，其中Φ和|g|的上升取决于手性阴离子中的电荷数和芳基取代基。利用毛细管中的软光刻微成型技术，我们可以制造出排列精致的一维共组装体，实现Φ为0.32和|g|为0.13的指标。最后，我们的光谱研究阐明了双重放大的潜在机制，在CPL活性发光体的发展方面取得了重大进展。
