ChemInform Abstract: Electronic Communication in Tetrathiafulvalene (TTF)/C60 Systems: Toward Molecular Solar Energy Conversion Materials?

Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense, E-28040 Madrid, Spain.
Accounts of Chemical Research (Impact Factor: 22.32). 11/2007; 40(10):1015-24. DOI: 10.1021/ar700026t
Source: PubMed


The covalent connection of the electron acceptor C 60 to p-quinonoid pi-extended tetrathiafulvalenes (exTTFs) has allowed for the preparation of new photo- and electroactive conjugates able to act as artificial photosynthetic systems and active molecular materials in organic photovoltaics. The gain of aromaticity undergone by the pi-extended TTF unit in the oxidation process results in highly stabilized radical ion pairs, namely, C 60 (*-)/exTTF (*+). Lifetimes for such charge-separated states, ranging from a few nanoseconds to hundreds of microseconds, have been achieved by rationally modifying the nature of the chemical spacers. These long-lived radical pairs are called to play an important role for the conversion of sunlight into chemical or electrical power.

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    • "TTF derivatives now play a significant role as redox sites in different areas of supramolecular chemistry. Some applications call for their use as cations sensors [7–9] as a π-electron donor for non-linear optical systems [10–12], heterocycles [13–15], integrated into polymeric [16–18] and dendritic systems [19] and used as a component for molecular electronic devices [20–22]. "
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    ABSTRACT: The synthesis of new unsymmetrically benzene-fused bis (tetrathiafulvalene) has been carried out by a cross-coupling reaction of the respective 4,5-dialkyl-1,3-dithiole-2-selenone 6-9 with 2-(4-(p-nitrophenyl)-1,3-dithiole-2-ylidene)-1,3,5,7-tetrathia-s-indacene-6-one 5 prepared by olefination of 4-(p-nitrophenyl)-1,3-dithiole-2-selenone 3 and 1,3,5,7-tetrathia-s-indacene-2,6-dione 4. The conversion of the nitro moiety 10a-d to amino 11a-d then dibenzylamine 12a-d groups respectively used reduction and alkylation methods. The electron donor ability of these new compounds has been measured by cyclic voltammetry (CV) technique. Charge transfer complexes with tetracyanoquino-dimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials.
    Full-text · Article · Mar 2014 · International Journal of Molecular Sciences
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    • "In this process, photons are absorbed and re-emitted, which results in the occurrence of energy relaxation from high energy wavelength to low energy wavelength. Therefore, these materials have wide applications including organic field-effect transistors [1], organic light-emitting diodes [2], organic photovoltaics [3] [4] [5] and biochemical sensors [6]. On the other hand, these ␲-conjugated compounds can also be used as wavelengthshifting materials to improve performance of cadmium telluride (CdTe) solar cells. "
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    ABSTRACT: A series of triphenylamine-based aromatic cyano compounds have been synthesized as red-emitting fluorophores with large Stokes shifts in both solution (>100 nm in CHCl3) and solid state (>150 nm in film). Intramolecular charge transfer (ICT) properties of the synthesized compounds are examined using UV–Vis absorptions, photoluminescence measurements and solvatochromic studies. Our studies suggest that Stokes shifts of these compounds can be fine-tuned by manipulating the ICT strength between donor and acceptor with various electronic donating groups, and the largest Stokes shifts are typically associated with compounds that have the strong ICT characters. The observed spectroscopic properties of the compounds are consistent with theoretical calculations using density function theory (DFT) or time-dependent density function theory (TD-DFT). The calculations suggest that the ICT occurs from localized HOMO to localized LUMO with magnitudes of 60–80%. The relative quantum yields of these fluorophores in solution are various and highly solvent dependent. In solid state, the quantum yields of the compounds are significantly increased and some can reach to 0.40.
    Full-text · Article · Jan 2013 · Journal of Photochemistry and Photobiology A Chemistry
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    • "The synthesis of compounds 1a–d from 4,7- dibromobenzo[c][1] [2] [5] "
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    ABSTRACT: The synthesized benzothiadiazole-based series fluorophores as potential wavelength-shifting materials exhibit large Stokes shifts (>160 nm) with multiple broad absorbance bands from UV region to 600 nm and a strong fluorescence peak around 700 nm (in CHCl3). Intramolecular charge transfer (ICT) characters of the synthesized compounds are examined using UV–vis and photoluminescence solvatochromic shift measurements. Among the synthesized compounds, the fluorophores with asymmetrical structures exhibit larger Stokes shifts than those with symmetrical structures due to large dipole moment changes upon excitation. The fluorophores with electron-donating methoxyl groups attached to the triphenylamine donors are found to have strong ICT properties. Photophysical experimental results are supported by theoretical calculations using Density Function Theory (DFT) and Time Dependent Density Function Theory (TD-DFT) methods. Calculated frontier molecular orbitals (MOs) of ground states on these fluorophores showed an increase in ICT character up to 50% from HOMO to LUMO. Geometric optimization calculations of the excited state reveal that these fluorophores show a more planar structure for the excited state than the ground state, which allows more π–π* overlap and leads to larger Stokes shifts and higher quantum yields.
    Full-text · Article · Mar 2012 · Journal of Photochemistry and Photobiology A Chemistry
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