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双发色团芘-PPV 低聚物体系中的光诱导能量转移:柔性给体-受体桥的作用。

Photoinduced energy transfer in bichromophoric pyrene-PPV oligomer systems: the role of flexible donor-acceptor bridges.

机构信息

Universidad Nacional Autónoma de México, Instituto de Química, Ciudad Universitaria, 04510, México, D.F., México.

出版信息

J Phys Chem B. 2012 Mar 22;116(11):3490-503. doi: 10.1021/jp208602q. Epub 2012 Mar 14.

Abstract

In this contribution, we report on the electronic energy transfer dynamics of bichromophoric systems incorporating two pyrene chromophores tethered by variable-length flexible alkyloxy chains to p-phenylenevinylene oligomers. These were studied using UV-vis absorption and both steady state and time-resolved fluorescence spectroscopy. Time-resolved emission measurements showed an efficient photoinduced energy transfer process in all the multichromophoric systems, which occurs on the time scale of tens of picoseconds after excitation at 265 nm. The energy transfer process is especially efficient in systems where the linker is formed by eight atoms (up to k(ET) ≈ 2.7 × 10(10) s(-1)), which, despite not being the shortest bridge studied, allows the approach of the donor and acceptor chromophores due to an appropriate number of flexible single bonds. Using Förster theory, we calculated the donor-acceptor distance in each triad from the experimental energy transfer rate, finding them to be in the range 8.8-10 Å.

摘要

在本研究中,我们报告了含有两个芘发色团的双发色团体系的电子能量转移动力学,该体系通过可变长度的柔性烷氧基链连接到对苯撑乙烯低聚物上。我们使用紫外-可见吸收光谱以及稳态和时间分辨荧光光谱对其进行了研究。时间分辨发射测量表明,在 265nm 激发后,所有多色团体系中都发生了有效的光诱导能量转移过程,该过程发生在数十皮秒的时间尺度内。在连接体由八个原子组成的体系中(高达 k(ET) ≈ 2.7 × 10(10) s(-1)),能量转移过程尤其有效,尽管这不是研究中最短的桥,但由于存在适当数量的柔性单键,允许供体和受体发色团接近。我们使用Förster 理论从实验能量转移速率计算了每个三联体中的供体-受体距离,发现它们在 8.8-10Å 范围内。

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