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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Switching of the photophysical properties of Bodipy-derived trans bis(tributylphosphine) Pt(II) bisacetylide complexes with rhodamine as the acid-activatable unit
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Switching of the photophysical properties of Bodipy-derived trans bis(tributylphosphine) Pt(II) bisacetylide complexes with rhodamine as the acid-activatable unit

机译：以罗丹明为酸可激活单元的Bodipy衍生的反式双（三丁基膦）Pt（II）双乙炔化物配合物的光物理性质的转换

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摘要

A rhodamine moiety was used for the preparation of trans bis(tributylphosphine) Pt(II) bisacetylide complexes (RH-BDPY-Pt-1 and RH-BDPY-Pt-2, with two different Bodipy acetylide ligands), which show acid/base-switchable photophysical properties. The rhodamine moiety undergoes reversible spirolactam. opened amide structure transformation in the presence of an acid/base. Bodipy ligands are responsible for strong visible light-harvesting. The photophysical properties of the Pt(II) complexes were studied with steady state UV-Vis absorption, luminescence spectra, nanosecond transient absorption spectroscopy, electrochemical characterization and DFT/TDDFT computations. In the absence of an acid, the complexes show the absorption of Bodipy ligands at 580 nm and 500 nm, respectively. Both complexes show fluorescence. A minor phosphorescence band was observed for RH-BDPY-Pt-1. In the presence of trifluoroacetic acid (TFA), the spirolactam. opened amide transformation occurred and the absorption of the rhodamine moiety at 570 nm appeared; colour changes were observed for the solutions of the complexes. Moreover, the fluorescence of the complexes was switched on. Long-lived triplet excited states were observed for the two complexes (35 mu s and 423 mu s, respectively, in dichloromethane). Upon the addition of TFA, the triplet state lifetime of RH-BDPY-Pt-1 was substantially prolonged to 80 mu s from 35 mu s (the triplet state of RH-BDPY-Pt-1 is localized on the Bodipy moiety); for RH-BDPY-Pt-2, however, the triplet state is switched from the Bodipy-confined triplet state to a triplet state delocalized on the Bodipy and rhodamine moiety. Thus both the singlet excited state and the triplet state of the Pt(II) complexes were switched upon the addition of an acid. The photophysical properties were rationalized with DFT/TDDFT calculations. These results on tuning of the photophysical properties of Pt(II) complexes with a rhodamine moiety may be useful for designing external stimuli-activatable transition metal complexes.
机译：罗丹明部分用于制备反式双（三丁基膦）Pt（II）双乙炔化物配合物（RH-BDPY-Pt-1和RH-BDPY-Pt-2，具有两个不同的Bodipy乙炔配体），其显示酸/碱可切换的光物理性质。罗丹明部分经历可逆的螺内酰胺。在酸/碱存在下打开酰胺结构转变。 Bodipy配体负责强大的可见光收集。利用稳态紫外-可见吸收，发光光谱，纳秒瞬态吸收光谱，电化学表征和DFT / TDDFT计算研究了Pt（II）配合物的光物理性质。在不存在酸的情况下，络合物分别显示Bodipy配体在580 nm和500 nm处的吸收。两种复合物均显示荧光。观察到RH-BDPY-Pt-1的次要磷光带。在三氟乙酸（TFA）存在下，螺内酰胺。发生酰胺开环转化，出现了若丹明部分在570 nm的吸收。观察到配合物溶液的颜色变化。此外，复合物的荧光被打开。观察到两种络合物的长寿命三重态激发态（在二氯甲烷中分别为35μs和423μs）。加入TFA后，RH-BDPY-Pt-1的三重态寿命从35μs基本延长至80μs（RH-BDPY-Pt-1的三重态位于Bodipy部分）;然而，对于RH-BDPY-Pt-2，三重态从Bodipy限制的三重态转换为Bodipy和若丹明部分上离域的三重态。因此，加入酸后，Pt（II）配合物的单重态和三重态都发生了变化。用DFT / TDDFT计算使光物理性质合理化。具有罗丹明部分的Pt（II）配合物的光物理性质调节的这些结果可用于设计外部刺激可激活的过渡金属配合物。

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