Supramolecular Ga4L612鈥?/sup> Cage Photosensitizes 1,3-Rearrangement of Encapsulated Guest via Photoinduced Electron Transfer

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• 作者：Derek M. Dalton ; Scott R. Ellis ; Eva M. Nichols ; Richard A. Mathies ; F. Dean Toste ; Robert G. Bergman ; Kenneth N. Raymond
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：August 19, 2015
• 年：2015
• 卷：137
• 期：32
• 页码：10128-10131
• 全文大小：331K
• ISSN：1520-5126

文摘

The K₁₂Ga₄L₆ supramolecular cage is photoactive and enables an unprecedented photoreaction not observed in bulk solution. Ga₄L₆^{12鈥?/sup> cages photosensitize the 1,3-rearrangement of encapsulated cinnamylammonium cation guests from the linear isomer to the higher energy branched isomer when irradiated with UVA light. The rearrangement requires light and guest encapsulation to occur. The Ga₄L₆12鈥?/sup> cage-mediated reaction mechanism was investigated by UV/vis absorption, fluorescence, ultrafast transient absorption, and electrochemical experiments. The results support a photoinduced electron transfer mechanism for the 1,3-rearrangement, in which the Ga₄L₆12鈥?/sup> cage absorbs photons and transfers an electron to the encapsulated cinnamylammonium ion, which undergoes C鈥揘 bond cleavage, followed by back electron transfer to the cage and recombination of the guest fragments to form the higher energy isomer.}