Pierre-Antoine Bouit

Efficient Electron Transfer and Sensitizer Regeneration in Stable π-extended Tetrathiafulvalene-Sensitized Solar Cells

The development of metal-free organic sensitizers is a key issue in dye-sensitized solar cell research. We report successful photovoltaic conversion with a new class of stable tetrathiafulvalene derivatives, showing surprising electrochemical and kinetic properties. With time-resolved spectroscopy we could observe highly efficient regeneration of the photo-oxidized tetrathiafulvalene sensitizers, which were attached to a mesoporous TiO(2) film, by a redox mediator in the pores (iodide/tri-iodide), even though the measured driving force for regeneration was only approximately 150 mV. This important proof-of-concept shows that sensitizers with a small driving force, i.e. the oxidation potential of the sensitizer is separated from the redox potenial of the mediator by as little as 150 mV, can operate functionally in dye-sensitized solar cells and eventually aid to reduce photovoltage losses due to poor energetic alignment of the materials.

Continuous Symmetry Breaking Induced by Ion Pairing Effect in Heptamethine Cyanine Dyes: Beyond the Cyanine Limit

The association of heptamethine cyanine cation 1(+) with various counterions A (A = Br(-), I(-), PF(6)(-), SbF(6)(-), B(C(6)F(5))(4)(-), TRISPHAT) was realized. The six different ion pairs have been characterized by X-ray diffraction, and their absorption properties were studied in polar (DCM) and apolar (toluene) solvents. A small, hard anion (Br(-)) is able to strongly polarize the polymethine chain, resulting in the stabilization of an asymmetric dipolar-like structure in the crystal and in nondissociating solvents. On the contrary, in more polar solvents or when it is associated with a bulky soft anion (TRISPHAT or B(C(6)F(5))(4)(-)), the same cyanine dye adopts preferentially the ideal polymethine state. The solid-state and solution absorption properties of heptamethine dyes are therefore strongly correlated to the nature of the counterion.

Benzofuran-fused Phosphole: Synthesis, Electronic, and Electroluminescence Properties

A synthetic route to novel benzofuran-fused phosphole derivatives 3-5 is described. These compounds showed optical and electrochemical properties that differ from their benzothiophene analog. Preliminary results show that 4 can be used as an emitter in OLEDs, illustrating the potential of these new compounds for opto-electronic applications.

A "cyanine-cyanine" salt exhibiting photovoltaic properties.

Association between cationic and anionic heptamethine dyes led to the formation of a new organic salt (3) displaying exceptional light-harvesting properties in the NIR spectral range and having amphoteric redox character. Preliminary results of molecular bulk heterojunction solar cells based on the title compound 3 and [60]PCBM as the only active layer reveal this new dye as a promising light-harvesting material for photovoltaics.

Excited state absorption: a key phenomenon for the improvement of biphotonic based optical limiting at telecommunication wavelengths

Spectroscopic properties, two-photon absorption (TPA) and excited state absorption (ESA), of two organic cyanine dyes and of a ruthenium based organometallic cyanine are compared in order to rationalize their similar ns-optical power limiting (OPL) efficiency in the telecommunication wavelength range. The TPA contribution to the ns-OPL behavior is higher for both organic cyanines, while the main process is a TPA-induced ESA in the case of the organometallic system, in which the ruthenium induces a broadening of the NIR-ESA band and resulting in a strong spectral overlap between TPA and ESA spectra.

Donor-π-acceptors containing the 10-(1,3-dithiol-2-ylidene)anthracene unit for dye-sensitized solar cells.

Two donor-acceptor molecular tweezers incorporating the 10-(1,3-dithiol-2-ylidene)anthracene unit as donor group and two cyanoacrylic units as accepting/anchoring groups are reported as metal-free sensitizers for dye-sensitized solar cells. By changing the phenyl spacer with 3,4-ethylenedioxythiophene (EDOT) units, the absorption spectrum of the sensitizer is red-shifted with a corresponding increase in the molar absorptivity. Density functional calculations confirmed the intramolecular charge-transfer nature of the lowest-energy absorption bands. The new dyes are highly distorted from planarity and are bound to the TiO(2) surface through the two anchoring groups in a unidentate binding form. A power-conversion efficiency of 3.7% was obtained with a volatile CH(3)CN-based electrolyte, under air mass 1.5 global sunlight. Photovoltage decay transients and ATR-FTIR measurements allowed us to understand the photovoltaic performance, as well as the surface binding, of these new sensitizers.

Tuning the electronic properties of nonplanar exTTF-based push-pull chromophores by aryl substitution.

A new family of π-extended tetrathiafulvalene (exTTF) donor-acceptor chromophores has been synthesized by [2 + 2] cycloaddition of TCNE with exTTF-substituted alkynes and subsequent cycloreversion. X-ray data and theoretical calculations, performed at the B3LYP/6-31G** level, show that the new chromophores exhibit highly distorted nonplanar molecular structures with largely twisted 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) units. The electronic and optical properties, investigated by UV/vis spectroscopy and electrochemical measurements, are significantly modified when the TCBD acceptor unit is substituted with a donor phenyl group, which increases the twisting of the TCBD units and reduces the conjugation between the two dicyanovinyl subunits. The introduction of phenyl substituents hampers the oxidation and reduction processes and, at the same time, largely increases the optical band gap. An effective electronic communication between the donor and acceptor units, although limited by the distorted molecular geometry, is evidenced both in the ground and in the excited electronic states. The electronic absorption spectra are characterized by low- to medium-intense charge-transfer bands that extend to the near-infrared.

Efficient Utilization of Higher-Lying Excited States to Trigger Charge-Transfer Events

Several new fullerene-heptamethine conjugates, which absorb as far as into the infrared spectrum as 800 nm, have been synthesized and fully characterized by physicochemical means. In terms of optical and electrochemical characteristics, appreciable electronic coupling between both electroactive species is deduced. The latter also reflect the excited-state features. To this end, time-resolved, transient absorption measurements revealed that photoexcitation is followed by a sequence of charge-transfer events which evolve from higher singlet excited states (i.e., S(2)--fast charge transfer) and the lowest singlet excited state of the heptamethine cyanine (i.e., S(1)--slow charge transfer), as the electron donor, to either a covalently linked C(60) or C(70), as the electron acceptor. Finally, charge transfer from photoexcited C(60)/C(70) completes the charge-transfer sequence. The slow internal conversion within the light-harvesting heptamethine cyanine and the strong electronic coupling between the individual constituents are particularly beneficial to this process.

ExTTF-based dyes absorbing over the whole visible spectrum.

New push-pull dyes featuring π-extended tetrathiafulvalene (exTTF) as the donor group and tricyanofuran (TCF) as the acceptor group were synthesized and characterized. Their broad absorption covers the entire visible spectral range and enters the near-infrared region. Electrochemistry and theoretical calculations provided an understanding of these singular electronic properties. The new dyes are appealing candidates as light harvesters in photovoltaic devices.

Efficient light harvesting anionic heptamethine cyanine–[60] and [70]fullerene hybrids

New anionic fullerene–heptamethine conjugates absorbing as far as 900 nm have been synthesized and fully characterized by physicochemical means. In terms of electron transfer, we have succeeded in realizing the rarely occurring scenario of a charge transfer commencing with a higher excited state. Kinetic studies reveal that charge separation and charge recombination dynamics occur in the normal and inverted Marcus region, respectively.