Arnold Mona E, Lebzelter Anika, Thielert Philipp, Blinder Rémi, Schmid Jonas, Zolg Julia, Spatola Emanuele, Jelezko Fedor, von Delius Max, Richert Sabine, Kuehne Alexander J C
Institute of Macromolecular and Organic Chemistry, Ulm University Albert-Einstein-Allee 11 89081 Ulm Germany
Institute of Physical Chemistry, University of Freiburg Albertstraße 21 79104 Freiburg Germany
Chem Sci. 2025 Jul 7. doi: 10.1039/d5sc03673a.
We present a new class of luminescent diradicals based on tris(trichlorophenyl)methyl (TTM) cores symmetrically bridged by indolocarbazole donors. These diradicals exhibit pure diradical character and unprecedented photoluminescence quantum yields of up to 18%, addressing key challenges in the development of stable, emissive organic diradicals. Light emitting diradicals represent a formidable challenge for synthetic chemists; for applications as molecular color centers in quantum sensing and as emitters in optoelectronics. Unlike conventional approaches that require the conversion of closed-shell precursors, we directly couple brominated TTM radicals Buchwald-Hartwig coupling. The magnetic and optical properties of the resulting molecules are comprehensively characterized by electron paramagnetic resonance EPR, UV-vis absorption, and photoluminescence spectroscopy. This work unites the robust photophysics of discrete TTM radicals with the electronic versatility of donor-bridged multi-spin systems, offering a promising design strategy for functional open-shell emitters.
我们展示了一类基于三(三氯苯基)甲基(TTM)核的新型发光双自由基,该核由吲哚并咔唑供体对称桥连。这些双自由基具有纯双自由基特性,以及高达18%的前所未有的光致发光量子产率,解决了稳定发光有机双自由基开发中的关键挑战。发光双自由基对合成化学家来说是一项艰巨的挑战;可应用于量子传感中的分子色心以及光电子学中的发光体。与需要将闭壳前体转化的传统方法不同,我们通过布赫瓦尔德-哈特维希偶联直接偶联溴化TTM自由基。通过电子顺磁共振(EPR)、紫外-可见吸收光谱和光致发光光谱对所得分子的磁性和光学性质进行了全面表征。这项工作将离散TTM自由基强大的光物理性质与供体桥连多自旋系统的电子多功能性结合起来,为功能性开壳发光体提供了一种有前景的设计策略。