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27 August 2003 Optical spectroscopy of single-molecule and aggregate hexabenzocoronene derivatives
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The low, medium and high concentration luminescence and luminescence-excitation spectra for alkyl substituted hexa-peri-hexabenzocoronene (HBC-C8,2) and hexa(4-n-dodecylphenyl) substituted hexa-peri-hexabenzocoronene (HBC-PhC12) are presented. A study of the concentration dependence of the optical properties of these self-assembling molecular nanowires, in the low to medium concentration regime, associates the spectrum at ~ 10-13 M with the single molecule, and indicates that previously published spectra of HBC's by others were the product of aggregation phenomena. The insertion of an exo-phenyl group between the HBC core and the alkyl side chains, as in HBC-PhC12, was found not to extend the conjugation, but did increase the inhomogeneous broadening of the single molecule luminescence. The continued presence of HBC-PhC12 single molecules, at high concentration, implies that HBC-C8,2 aggregates are thermodynamically more stable than HBC-PhC12 aggregates. In conclusion, the spectroscopic properties of both derivatives were found to be very sensitive to aggregation at low concentration and strongly correlated to the observed macroscopic physical properties.
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Alexander John Fleming, Jonathan N. Coleman, Alan Brian Dalton, Andreas Fechtenkoetter, Mark D. Watson, Klaus Muellen, Hugh James Byrne, and Werner J. Blau "Optical spectroscopy of single-molecule and aggregate hexabenzocoronene derivatives", Proc. SPIE 4876, Opto-Ireland 2002: Optics and Photonics Technologies and Applications, (27 August 2003);

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