Near-infrared absorption of fused core-modified expanded porphyrins for dye-sensitized solar cells.

Photophysical, photovoltaic, and charge transport properties of fused core-modified expanded porphyrins containing two pyrroles, one dithienothiophene (DTT) unit, and 1-4 thiophenes (1-4) were inspected by using density functional theory (DFT) and time-dependent DFT. Compounds 1-3 have been investigated experimentally before, but 4 is a theoretical proposal whose photophysical features match those extrapolated from 1 to 3. They exhibit absorption in the range of 700-970 nm for their Q bands and 500-645 nm for their Soret bands. The rise of thiophene rings placed in front of the DTT unit in the expanded porphyrin ring causes a bathochromic shift of the longest absorption wavelength, leading to near-infrared absorptions, which represent 49% of the solar energy. All the systems show a thermodynamically favorable process for the electron injection from the dye to TiO2 and adsorption on a finite TiO2 model. The electron regeneration of the dye is only thermodynamically feasible for the smallest expanded porphyrins 1 and 2 when I-/I3- electrolyte is used. The charge transport study shows that for voltages lower than 0.4 V, junctions featuring pentaphyrin 1 and octaphyrin 4 are more conductive than those containing hexaphyrin 2 or heptaphyrin 3. The results showed that the four fused core-modified expanded porphyrins investigated are potential dyes for applications in dye-sensitized solar cells, mainly pentaphyrin 1 and hexaphyrin 2. Moreover, increasing the number of thiophene rings in the macrocycle proved fruitful in favoring absorption in the near-infrared region, which is highly desired for dye-sensitized solar cells.

Fullerene binding effects in Al(III)/Zn(II) Porphyrin/Phthalocyanine photophysical properties and charge transport.

We evaluate the fullerene C60 binding effect; through the metal (Al) and through the ligand (Pc,TPP), on the photophysical and charge transport properties of M-porphyrin(TPP)/phthalocyanine(Pc) (M = Al(III), Zn(II)). We perform density functional theory (DFT) and time-dependent DFT calculations for the macrocycle-C60 dyads, showing that all systems studied are thermodynamically favorable. The C60 binding effect on the absorption spectrum is a red-shift of the Q and Soret (B) bands of TPPs and Pcs. The Pc-dyads show longer λ for Q bands (673 nm) than those with TPP (568 nm). AlTPP-C60 and ZnTPP-C60 show a more favorable electron injection to TiO2 than the analogs Pcs, and the regeneration of the dye is preferred in AlTPP-C60 and AlPc-C60. Zero-bias conductance is computed (10-4-10-7 G0) for the dyads using molecular junctions with Au(111)-based electrodes. When a bias voltage of around 0.6 V up to 1 V is applied, an increase in current is obtained for AlTPP-C60 (10-7 A), ZnTPP-C60 (10-7 A), and AlPc-C60 (10-8 A). Although there is not a unique trend in the behavior of the dyads, Pcs have better photophysical properties than TPPs and the latter are better in the charge transport. We conclude that AlTPP(ZnTPP)-C60 dyads are an excellent alternative for designing new materials for dye-sensitized solar cells or optoelectronic devices.

A photo-induced spin crossover based molecular switch and spin filter operating at room temperature.

Since Venkataramani et al. (Science, 2011, 331(6016), 445-448) reported reversible, room-temperature light-induced spin crossover in Ni-porphyrin functionalized with a phenylazopyridine ligand (NiTPP-PAPy), this complex has attracted the attention of many researchers due to its potential applications in molecular-based devices. In this work, we perform a detailed study, by means of DFT and WFT methodologies, focused on the deposition of NiTP-PAPy over an Au(111) surface, followed by DFT-NEGF calculations employing a gold surface and the tip of an STM as electrodes, in order to probe the deposited complex's transport properties. Our DFT calculations show that not only the metalled porphyrin is strongly adsorbed on the surface, in both the high (HS) and low spin (LS) configurations, but also, and more importantly, photoinduced switching is preserved upon adsorption, a fact that is also confirmed through WFT and TD-DFT calculations. Moreover, our DFT-NEGF calculations indicate that the current passing through the molecular junction-like systems is much higher in the HS configuration than in the LS one, along with the fact that the current calculated in the ferromagnetic junction is highly spin-polarized. These remarkable transport properties suggest that the complex could be used as a component in molecular switches based on the total current passing through the system, modulated by light irradiation, spin filters due to the spin polarization of the carriers in the HS configuration, or even in two-step rectifiers combining the two features mentioned above, all of these operating at room temperature, giving to this complex the potential to be an active element in all kinds of future spintronic devices.

A comparison of computational methodologies for the structural modelling of biologically relevant zinc complexes.

The impact of a variety of modern computational methods on the structure of biologically relevant zinc complexes is studied. Different density functionals and a Hartree-Fock-based method, scalar-relativistic effects, and basis set integration grid choices, among others, are assessed for set of high-resolution crystallographic structures. While a previous study recommends incorporating relativistic effects into density functional theory calculations in order to improve the accuracy of obtained geometries for small Zn(II) coordination compounds, we show that, for the set in study, relativistic effects do not affect the geometries to a significant extent. The PBEh-3c composite method emerges as good alternative for the treatment of Zn(II) complexes, while the HF-3c method can be employed when computational efficiency is important. Graphical Abstract Which methods are best suited for the computation of Zn(II) bioligand complexes?

Reacción de reducción de Cr(VI) a Cr(III) por iones sulfito en presencia de iones fosfato / Reduction reaction of Cr(VI) to Cr(III) by sulfite ions in the presence of phosphate ions

La sinovitis crónica, complicación frecuente en artritis reumatoide y hemofi lia, es tratada con éxito mediante inyecciones intrarticulares de dispersiones radiactivas (Radiosinoviortesis). En Cuba está en uso una formulación de Fosfato Crómico marcado con . A fin de aumentar el escalado, perfeccionar la tecnología y obtener formulaciones con otros radionúclidos, se estudia la reacción de obtención del precipitado, basada en la reducción de Cr(VI) a Cr(III) con iones sulfito en presencia de iones fosfato. Si la relación / es 18.5 veces, la precipitación tiene lugar próximo a las dos horas a temperatura ambiente y el pH crece al inicio y permanece luego constante a 7.63 por acción buffer del sulfito. Se estableció que la reducción de Cr(VI) a Cr(III) a ese pH sigue una reacción de segundo orden. La formación de especies insolubles de cromo y fósforo favorece la reducción. A 70 ºC la precipitación ocurre de inmediato. Por el método de los indicadores radiactivos se establece que la relación Cr/P = 1.6 en el precipitado, tanto a temperatura ambiente como a 70 ºC. En este caso, cada componente de la razón y la masa disminuyen en un 8 %, lo que indica probablemente se trate de un solo producto. El calor acelera la formación del precipitado y lo disuelve en parte. Si / = 1.5, el precipitado se forma de inmediato a temperatura ambiente alrededor de pH 5. Bajo las condiciones utilizadas, las especies de cromo en el precipitado aumentan con el pH. Se sugieren posibles composiciones para los productos obtenidos.

Chronic sinovitis, a frequent complication in rheumatoid arthritis and hemophilia, is successfully treated by means of intrarticular injections of radioactive dispersions (Radiosynoviorthesis). In Cuba, a formulation of chromic phosphate labeled with is used. In order to scale up the process, improve the technology and obtain formulations with other radionuclides, the reaction, based on the reduction of Cr(VI) to Cr(III) with sulphite ions in presence of ions phosphate is studied. If the relationship / is 18.5 times, the precipitation takes place at room temperature roughly at two hours and the pH increases at the beginning and then remains constant at 7.63 because of the buffer action of the sulphite. It was established that the reduction of Cr(VI) to Cr(III) at this pH is a second order reaction. The formation of insoluble species of chromium and phosphor, favors the reduction. At 70 ºC the precipitation occurs immediately. Using the method of radioactive indicators, it was established that the relationship Cr/P in the precipitate, at room temperature and at 70 ºC is 1.6. In this case, each component of the relationship and the mass diminish in 8 %, which indicates we are probably in presence of the same product. The heat accelerates the formation of the precipitate and partially dissolves it. If / = 1.5, and the pH value around 5, the precipitate is formed immediately at room temperature. Under the used experimental conditions, the chromium species in the precipitate increase as the pH increases. Possible compositions for the obtained products are suggested.