Gas‐Phase Ion Fluorescence Spectroscopy of Tailor‐made Rhodamine Homo‐ and Heterodyads: Quenching of Electronic Communication by π‐Conjugated Linkers,Angewandte Chemie International Edition

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Gas‐Phase Ion Fluorescence Spectroscopy of Tailor‐made Rhodamine Homo‐ and Heterodyads: Quenching of Electronic Communication by π‐Conjugated Linkers
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-08-13 , DOI: 10.1002/anie.202008314
Anne Ugleholdt Petersen ₁ , Christina Kjær ₂ , Cecilie Jensen ₁ , Mogens Brøndsted Nielsen ₁ , Steen Brøndsted Nielsen ₂

Affiliation

While many key photophysical features are understood for electronic communication between chromophores in neutral compounds, there is limited information on the effect of charges in practically relevant ionic chromo/fluorophores. Here we have chosen positively charged rhodamines and prepared a selection of homo‐ and heterodimers with alkyl or π‐conjugated, acetylenic bridges. Protonated molecules were transferred as isolated ions to gas phase where there is no solvent screening of charges, and fluorescence spectra were measured with a custom‐made ion‐trap setup. Our work reveals strong polarization of the π‐spacer (induced dipole/quadrupole) when it experiences the electric field from one/ two dyes. Hence, π‐spacers provide efficient shielding of charges by reducing the Coulomb interaction, whereas two dye cations polarize each other when connected by an alkyl. The screening influences the Förster resonance energy transfer efficiency that relies on the dipole–dipole interaction.

中文翻译：

量身定制的若丹明同质和外差体的气相离子荧光光谱：π共轭连接子对电子通信的猝灭

虽然中性化合物中生色团之间的电子通讯理解了许多关键的光物理特征，但有关电荷在实际相关的离子发色团/荧光团中的作用的信息有限。在这里，我们选择了带正电荷的若丹明，并准备了具有烷基或π共轭炔键的同二聚体和异二聚体。质子化的分子作为分离的离子转移到气相中，而没有溶剂筛选电荷，并且使用定制的离子阱装置测量了荧光光谱。我们的工作揭示了当受到一种/两种染料的电场作用时，π-间隔子（感应偶极/四极子）的强烈极化。因此，π间隔子通过减少库仑相互作用来提供对电荷的有效屏蔽，而两个染料阳离子通过烷基连接时会相互极化。屏蔽影响依赖偶极-偶极相互作用的福斯特共振能量转移效率。

更新日期：2020-08-13

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