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Variable-Gap Conjugated Oligomers Grafted to CdSe Nanocrystals

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journal contribution
posted on 28.08.2012, 00:00 by Romain Stalder, Dongping Xie, Renjia Zhou, Jiangeng Xue, John R. Reynolds, Kirk S. Schanze
Three linear asymmetrically functionalized conjugated molecules composed of five or six aromatic rings were synthesized, bearing a terminal phosphonic acid group, with the objective of enabling their grafting onto inorganic CdSe nanocrystals. These chromophoresoligo­(phenylene ethynylenes), oligothiophenes, or donor–acceptor–donor oligothiophenes with a benzothiadiazole acceptorwere designed with decreasing HOMO–LUMO energy gaps such that increasing amounts of light could be absorbed toward the longer wavelengths up to 600 nm. Electrochemical measurements show that the energy offsets between the HOMO and LUMO energies of the organic molecules and the energy bands of the CdSe nanocrystals are well-suited for charge transfer between the organic and inorganic components. The characteristics of each component’s excited state are studied by fluorescence spectroscopy and the interaction between the conjugated molecules and the CdSe nanocrystals in dilute solutions is monitored by photoluminescence quenching. In the latter experiments, where ester and acid derivatives are compared, the pronounced difference in luminescence quenching supports the ability of the phosphonic acid groups to strongly anchor onto the surface of the nanocrystals. Moreover, these results suggest that charge transfer likely occurs between the organic and the inorganic compounds, and appropriate ratios for the corresponding organic/inorganic hybrids preparation are identified. The preparation by direct ligand exchange and the photophysical properties of the hybrids are described, and spectroscopic analysis estimates that the nanocrystals are covered, on average, with 100–200 electroactive organic molecules. The incident photon-to-electron conversion efficiency reflects the solution absorption of the hybrids because it shows the response from both organic and inorganic components.