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  • Title: Spectroscopic properties of nanotube-chromophore hybrids.
    Author: Huang C, Wang RK, Wong BM, McGee DJ, Léonard F, Kim YJ, Johnson KF, Arnold MS, Eriksson MA, Gopalan P.
    Journal: ACS Nano; 2011 Oct 25; 5(10):7767-74. PubMed ID: 21919456.
    Abstract:
    Recently, individual single-walled carbon nanotubes (SWNTs) functionalized with azo-benzene chromophores were shown to form a new class of hybrid nanomaterials for optoelectronics applications. Here we use a number of experimental and computational techniques to understand the binding, orientation, and nature of coupling between chromophores and the nanotubes, all of which are relevant to future optimization of these hybrid materials. We find that the binding energy between chromophores and nanotubes depends strongly on the type of tether that is used to bind the chromophores to the nanotubes. The pyrene tethers form a much stronger attachment to nanotubes compared to anthracene or benzene rings, resulting in more than 80% retention of bound chromophores post-processing. Density functional theory (DFT) calculations show that the binding energy of the chromophores to the nanotubes is maximized for chromophores parallel to the nanotube sidewall, even with the use of tethers; optical second harmonic generation measurements show that there is nonetheless a partial radial orientation of the chromophores on the nanotubes. We find weak electronic coupling between the chromophores and the SWNTs, consistent with noncovalent binding. This weak coupling is still sufficient to quench the chromophore fluorescence through a combination of static and dynamic processes. Photoluminescence measurements show a lack of significant energy transfer from the chromophores to isolated semiconducting nanotubes.
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