Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation
Pyrene-Functionalized Ruthenium Nanoparticles: Novel Fluorescence Characteristics from Intraparticle Extended Conjugation
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DOI：
10.1021/jp906874f
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发表时间：
2009-09
影响因子：
3.7
通讯作者：
Wei Chen;N. Zuckerman;J. Lewis;J. Konopelski;Shaowei Chen
中科院分区：
文献类型：
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作者：
Wei Chen;N. Zuckerman;J. Lewis;J. Konopelski;Shaowei Chen
通过卡宾稳定的纳米粒子与1-乙烯基芘和1-烯丙基芘(分别称为Ru═VPy和Ru═APY)的烯烃歧化反应，制备了含Py基团的纳米Ru。核磁共振氢谱测定结果表明，所合成化合物的表面浓度分别为26.4%和22.9%。在荧光测量中，Ru═VPy纳米粒子在392和490 nm处有两个明显的发射带，与(E)-1，2-二(吡喃-1-基)乙烯的发射带非常相似，这表明颗粒结合的芘部分可能通过Ru═卡宾π键而表现为具有共轭连接基的二聚体。与之形成鲜明对比的是，Ru═APY纳米粒子在392 nm处只有一个发射峰，与1-乙烯基芘和1-烯丙基芘的单体芘衍生物一致。这表明，通过将SP3碳插入到与Py基团结合的化学连接物中，可以有效地关闭颗粒内延伸共轭。
Ruthenium nanoparticles functionalized with pyrene moieties were prepared by olefin metathesis reactions of carbene-stabilized nanoparticles with 1-vinylpyrene and 1-allylpyrene (referred to as Ru═VPy and Ru═APy, respectively). 1H NMR spectroscopic measurements showed that the surface concentration of the pyrene moieties was 26.4 and 22.9%, respectively. In fluorescence measurements, Ru═VPy nanoparticles exhibited two prominent emission bands at 392 and 490 nm, very similar to those of (E)-1,2-di(pyren-1-yl)ethene, suggesting that the particle-bound pyrene moieties might behave equivalently to pyrene dimers with a conjugated linker by virtue of the Ru═carbene π bonds. In sharp contrast, Ru═APy nanoparticles displayed only a single emission peak at 392 nm, consistent with monomeric pyrene derivatives of 1-vinylpyrene and 1-allylpyrene. This implies that the intraparticle extended conjugation might be effectively turned off by the insertion of an sp3 carbon into the chemical linker that bound the pyrene moi...