Gusev Alexey, Kiskin Mikhail, Braga Elena, Zamnius Ekaterina, Kryukova Mariya, Karaush-Karmazin Nataliya, Baryshnikov Glib, Minaev Boris, Linert Wolfgang
V.I. Vernadsky Crimean Federal University Simferopol 295007 Crimea
N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences Moscow 119991 Russia.
RSC Adv. 2023 Jan 27;13(6):3899-3909. doi: 10.1039/d2ra06986e. eCollection 2023 Jan 24.
A new series of five highly emissive binuclear heteroleptic pyridyltriazole-Cu(i)-phosphine complexes 1-5 was synthesized and examined by different experimental (IR, elemental and thermogravimetric analysis, single crystal X-ray diffraction technique, UV-vis and fluorescence spectroscopy) and quantum chemical aproaches. Complexes 1-5 exhibited excellent stimuli-responsive photoluminescent performance in the solid state at room temperature (quantum yield (QY) = 27.5-52.0%; lifetime () = 8.3-10.7 μs) and when the temperature was lowered to 77 K (QY = 38.3-88.2; = 17.8-134.7 μs). The highest QY was examined for complex 3 (52%) that can be explained by the small structural changes between the ground S and exited S and T states leading to the small S-T triplet gap and efficient thermally-activated delayed fluorescence. Moreover, complex 4 demonstrates reversible mechanochromic and excitation dependent luminescence.
合成了一系列新的五个高发射性双核杂配吡啶基三唑-Cu(i)-膦配合物1-5，并通过不同的实验方法（红外光谱、元素分析和热重分析、单晶X射线衍射技术、紫外可见光谱和荧光光谱）以及量子化学方法对其进行了研究。配合物1-5在室温固态下（量子产率（QY）=27.5-52.0%；寿命（τ）=8.3-10.7μs）以及温度降至77K时（QY=38.3-88.2；τ=17.8-134.7μs）表现出优异的刺激响应光致发光性能。配合物3的量子产率最高（52%），这可以通过基态S和激发态S及T态之间的微小结构变化来解释，这种变化导致了较小的S-T三重态能隙和有效的热激活延迟荧光。此外，配合物4表现出可逆的机械变色和激发依赖发光。
