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Energy Transfer Processes in the Excited States of an {Ir(N C)2(N N)+‐Rhodamine} Dyad: An Experimental and Theoretical Study

机译:{Ir(N C)2(N N)+‐罗丹明}二元组激发态下的能量转移过程:实验和理论研究

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Abstract Herein we report the synthesis, characterization, photophysical and theoretical study of the luminescent dyad Ir‐RhB containing two emissive centers: The first fluorescent (RhB=rhodamine B) and the second phosphorescent (Ir=orthometalated iridium complex), bound with an aliphatic bridge. These nearly independent chromophores have triplet excited states which are very close in terms of energy, allowing for reversible energy transfer between them. The observed transient absorption spectra and their time dependent variations were interpreted in terms of a relatively simple kinetic model, where selective excitation of the iridium‐based chromophore affords the corresponding emissive triplet state, followed by its equilibration with the rhodamine based triplet state and simultaneous emissive relaxation to the dyad ground state. This model allows for analytical solution to give key characteristics of the dyad excited‐state dynamics, including the energy gap between these triplets (ΔE=0.017 eV) and the rate constant of energy transfer (k(Ir‐RhB)=6.0 ⋅ 108 s−1). These data were also verified by quantum chemical DFT and TD‐DFT calculations.
机译:摘要我们在此报告合成,特征,物理和理论研究发光双红外RhB包含两个发射中心:第一个荧光(RhB =罗丹明B)和第二磷光(Ir = orthometalated铱复杂),绑定一种脂肪族的桥。发色团有三重激发态很近就能源而言,允许吗他们之间可逆能量转移。观察到瞬态吸收光谱及其与时间有关的解释在变化一个相对简单的动力学模型,在哪里选择性激发的铱的基础发色团提供相应的发射三重态,其次是它的平衡基于罗丹明的三重态同时双发射松弛基态。解决方案给二分体的关键特征兴奋状态应承担的动力学,包括能源缺口这三胞胎之间(ΔE = 0.017 eV)和利率恒定的能量转移(k(红外必经RhB) = 6.0 108年代⋅−1)。验证了量子化学DFT和TD DFT计算。

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