Energy and charge transfer dynamics in fully decorated benzyl ether dendrimers and their disubstituted analogues

We examine the photophysics of a series of molecules consisting of a benzthiadiazole core surrounded by a network of benzyl ether arms terminated by aminopyrene chromophores, which function as both energy and electron donors. Three classes of molecules are studied: dendrimers whose peripheries are fully decorated with aminopyrene donors (F), disubstituted dendrimers whose peripheries contain only two donors (D), and linear analogues in which a pair of benzyl ether arms link two donors to the central core (L). The electronic energy transfer (EET) and charge transfer (CT) rates are determined by fluorescence lifetime measurements on the energy donors and electron acceptors, respectively. In all three types of molecules, the EET time scales as the square root of the generation number G, consistent with the flexible nature of the benzyl ether framework. Transient anisotropy measurements confirm that donor-donor energy hopping does not play a major role in determining the EET times. The CT dynamics occur on the nanosecond time scale and lead to stretched exponential decays, probably due to conformational disorder. Measurements at 100 degrees C confirm that conformational fluctuations play a role in the CT dynamics. The average CT time increases with G in the L and D molecules but decreases for the F dendrimers. This divergent behavior as G increases is attributed to the competing effects of larger donor-acceptor distances (which lengthen the CT time) versus a larger number of donors (which shorten the average CT time). This work illustrates two important points about light-harvesting and charge-separation dendrimers. First, the use of a flexible dendrimer framework can lead to a more favorable scaling of the EET time (and thus the light-harvesting efficiency) with dendrimer size, relative to what would be expected for a fully extended dendrimer. Second, fully decorated dendrimers can compensate for the distance-dependent slowdown in CT rate as G increases by providing additional pathways for the CT reaction to occur

Novel fluorescent security marker. Part I: morphological and optical properties of 2-amino-6-ethoxy-4-[4-(4- morpholinyl)phenyl]-3,5-pyridinedicarbonitrile nanoparticles

Newly synthesized fluorescent nanoparti- cles of 2-amino-6-ethoxy-4-[4-(4-morpholinyl)phenyl]-3, 5-pyridinedicarbonitrile have been developed and characterized for possible applications as security marker in paper documents. Nanoparticles have been prepared by reprecipitation in water under sonication. The size and the shape of these nanoparticles, charac- terized by light scattering and atomic force micros- copy, have been found to be highly dependent on sonication power. Typical sizes range from tens to hundreds of nanometers. Furthermore, a remarkable increase in the fluorescence yield has been observed as nanoparticles sizes decrease. Finally, all of the above features, together with the striking stability of optical and mechanical properties over the course of months, allow for straightforward applications that rely on strong and stable fluorescence such as marking impor- tant or valuable documents