Nuin Edurne, Sastre German, Pischel Uwe, Andreu Inmaculada, Miranda Miguel A
Instituto de Tecnología Química UPV-CSIC, Universitat Politècnica de València, Avenida de los Naranjos s/n, 46022 Valencia (Spain), Fax: (+34) 96-387-9444.
CIQSO-Centro de Investigación en Química Sostenible y Departamento de Ingeniería Química, Química Física y Química Orgánica, Universidad de Huelva, Campus de El Carmen s/n, 21071 Huelva (Spain).
Chemistry. 2015 Sep 7;21(37):12940-6. doi: 10.1002/chem.201501008. Epub 2015 Jul 23.
Novel diastereomeric triads containing two naphthalene chromophores have been designed in which an electron-donating amine moiety is covalently integrated into the connecting bridge. Photophysical studies (steady-state and time-resolved fluorescence) in solvents of different polarity have been performed. A remarkable stereodifferentiation in the intramolecular fluorescence quenching was found in acetonitrile. Laser flash photolysis gave rise to naphthalene-derived radical cations, which were also quenched by the amine with an even higher degree of stereodifferentiation. The results are in agreement with thermodynamic estimations and indicate that photoinduced electron transfer (PET) is the main quenching pathway. Furthermore, theoretical calculations have allowed us to explain the experimentally observed stereodifferentiation in PET quenching.
已设计出含有两个萘发色团的新型非对映三联体，其中一个供电子胺部分共价整合到连接桥中。已在不同极性的溶剂中进行了光物理研究（稳态和时间分辨荧光）。在乙腈中发现分子内荧光猝灭存在显著的立体分化。激光闪光光解产生了萘衍生的自由基阳离子，其也被胺猝灭，且立体分化程度更高。结果与热力学估计一致，表明光诱导电子转移（PET）是主要的猝灭途径。此外，理论计算使我们能够解释PET猝灭中实验观察到的立体分化。
