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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Linkage Dependence of Intramolecular Fluorescence Quenching Process in Porphyrin-Appended Mixed (Phthalocyaninato)(Porphyrinato) Yttrium(III) Double-Decker Complexes
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Linkage Dependence of Intramolecular Fluorescence Quenching Process in Porphyrin-Appended Mixed (Phthalocyaninato)(Porphyrinato) Yttrium(III) Double-Decker Complexes

机译：卟啉添加的混合酞菁（Porphyrinato）钇（III）双层配合物的分子内荧光猝灭过程的联系依赖性。

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摘要

Three novel mixed (phthalocyaninato)(porphyrinato) yttrium double-decker complexes appended with one metal-free porphyrin chromophore at the para. meta. and ortho position, respectively, of one meso-phenyl group of the porphyrin ligand in the double-decker unit through ester linkage, 3-5, have been designed, synthesized, and spectroscopically characterized. The photophysical properties of these three isomeric tetrapyrrole triads were comparatively investigated along with the model compounds metal-free tetrakis(4-butyl)porphyrin H2TBPP (1) and mixed [ 1,4,8,11,15,18,22,25-octakis(butyloxyl)phthalocyaninato][tetrakis(4-butyl)porphyrinato] yttrium double-decker complex HY[Pc(α-OC4H9)8](TBPP) (2) by steady-state and transient spectroscopic methods. The fluorescence of the metal-free porphyrin moiety attached through ester linkage at the meta and ortho position of one meso-phenyl group of porphyrin ligand in the double-decker unit in triads 4 and 5 is effectively quenched by the double-decker unit, which takes place in several hundred femtoseconds. However, the fluorescence of the metal-free porphyrin moiety attached at the para position of one meso-phenyl group of porphyrin ligand in the double-decker unit in triad 3 is only partially quenched, clearly revealing the effect of the position of porphyrin-substituent on the photophysical properties of the triads. Furthermore, the molecular structures of 3-5 were simulated using density functional theory calculations. It was found that the relative orientation between the metal-free porphyrin moiety and the double-decker unit for compound 3 is crossed, while those for compounds 4 and 5 are open- and closed-shellfish-like, respectively, which is suggested to be responsible for their different intramolecular fluorescent quenching efficiency.
机译：三种新型混合（邻苯二甲腈基）（卟啉纳）钇双层配合物，在对位附加了一种无金属的卟啉发色团。元通过酯键连接的双层单元中的卟啉配体的一个中位苯基的卟啉配位基和邻位分别被设计，合成和光谱表征。与不含金属的四（4-丁基）卟啉H2TBPP（1）和混合[1,4,8,11,15,18,22,25-稳态和瞬态光谱法研究八（丁基氧基）酞菁钠[四（4-丁基）卟啉酮]钇双层配合物HY [Pc（α-OC4H9）8]（TBPP）（2）。在三单元组4和5的双层单元中，通过酯键连接在卟啉配体的一个内消旋基团的间位和邻位的无金属卟啉部分的荧光被三单元组有效淬灭。发生在几百飞秒内。但是，在三单元组3的双层单元中，连接在卟啉配体的一个内消旋基团的对位上的无金属卟啉部分的荧光仅被部分淬灭，这清楚地揭示了卟啉取代基位置的影响关于三合会的光物理性质。此外，使用密度泛函理论计算模拟了3-5的分子结构。发现化合物3的无金属卟啉部分和双层单元之间的相对方向是交叉的，而化合物4和5的则是敞开的和闭壳的，这是建议的。负责他们不同的分子内荧光猝灭效率。

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