Mani Tomoyasu, Tanabe Mana, Yamauchi Seigo, Tkachenko Nikolai V, Vinogradov Sergei A
†Department of Biochemistry and Biophysics, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
‡Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan.
J Phys Chem Lett. 2012 Nov 1;3(21):3115-9. doi: 10.1021/jz301166e. Epub 2012 Oct 12.
Magnetic control over excited states of molecules presents interest for many applications. Here we show for the first time that visible room temperature phosphorescence in multichromophoric donor-acceptor systems can be modulated by weak magnetic fields (<1 T) via magnetic field effects (MFE) on the spin dynamics in photogenerated radical pairs (RPs). The studied compounds comprise Pt porphyrin (PtP)-Rosamine B (RosB) dyads, which possess strong visible absorption bands and phosphoresce at room temperature. The observed MFE is unique in that it occurs upon direct excitation of the PtP in the dyads, whereby ultrafast quantitative formation of the local PtP triplet state precedes the occurrence of radical intermediates. A model explaining the effect is proposed, which is based on reversible electron transfer between the local triplet state and a long-lived RP. External magnetic field modulates spin dynamics in the RP, affecting contribution of the singlet RP recombination channel and thereby influencing phosphorescence.
分子激发态的磁控在许多应用中都备受关注。在此,我们首次表明,在多发色团供体-受体体系中,可见光室温磷光可通过弱磁场(<1 T)对光生自由基对(RP)自旋动力学的磁场效应(MFE)进行调制。所研究的化合物包括铂卟啉(PtP)-玫瑰胺B(RosB)二元体系,其具有强烈的可见光吸收带且在室温下能发出磷光。观察到的MFE的独特之处在于,它发生在二元体系中PtP的直接激发时,由此在自由基中间体出现之前,超快定量地形成了局部PtP三重态。我们提出了一个解释该效应的模型,该模型基于局部三重态与长寿命RP之间的可逆电子转移。外部磁场调制RP中的自旋动力学,影响单线态RP复合通道的贡献,从而影响磷光。