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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Effects of proximity on the relaxation dynamics of flindersine and 6(5H)-phenanthridinone
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Effects of proximity on the relaxation dynamics of flindersine and 6(5H)-phenanthridinone

机译：邻近度对芬达素和6（5H）-菲啶酮的松弛动力学的影响

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摘要

The role played by the carbonyl group in the antenna system of a naturally occurring photochromic chromene, flindersine (FL), has been experimentally investigated and compared with that of a carbonyl group present in a structurally related unreactive heterocyclic compound, 6(5H)-phenanthridinone (PH). Through stationary and time-resolved absorption and emission techniques, the excited-state relaxation dynamics after UV irradiation were determined for FL and PH. The presence of a carbonyl group in both compounds entails the existence of two close-lying, strongly coupled electronic excited states, having n,pi* and pi,pi* character, respectively. Their coupling can be modulated by a careful choice of the solvent proticity and temperature. Moreover, in the case of strong coupling between the n,pi* and pi,pi* states, we have proved that the relaxation dynamics can involve transitions in which the upper of the coupled states acts as an intermediate for radiationless decay, bypassing the lowest emissive state, whereby the fluorescence quantum yield becomes a function of the excitation wavelength.
机译：已通过实验研究了羰基在天然存在的光致变色二甲基苯胺（FL）的天线系统中的作用并将其与结构相关的非反应性杂环化合物6（5H）-菲啶酮中存在的羰基的作用进行了比较（PH）。通过固定的和时间分辨的吸收和发射技术，确定了紫外线和荧光强度在紫外线照射后的激发态弛豫动力学。在两种化合物中羰基的存在意味着必须存在两个紧密，强耦合的电子激发态，分别具有n，pi *和pi，pi *特征。可以通过仔细选择溶剂的性质和温度来调节它们的偶联。此外，在n，pi *和pi，pi *状态之间存在强耦合的情况下，我们已经证明，弛豫动力学可能涉及跃迁，在跃迁中，耦合状态的上层充当无辐射衰变的中间层，绕过了最低的发射态，荧光量子产率成为激发波长的函数。

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