Platinum chromophore-based systems for photoinduced charge separation: a molecular design approach for artificial photosynthesis

Photoinduced charge separation is a fundamental step in photochemical energy conversion. In the design of molecularly based systems for light-to-chemical energy conversion, this step is studied through the construction of two- and three-component systems (dyads and triads) having suitable electron donor and acceptor moieties placed at specific positions on a charge-transfer chromophore. The most extensively studied chromophores in this regard are ruthenium(II) tris(diimine) systems with a common 3MLCT excited state, as well as related ruthenium(II) bis(terpyridyl) systems. This Forum contribution focuses on dyads and triads of an alternative chromophore, namely, platinum(II) di- and triimine systems having acetylide ligands. These d8 chromophores all possess a 3MLCT excited state in which the lowest unoccupied molecular orbital is a pi orbital on the heterocyclic aromatic ligand. The excited-state energies of these Pt(II) chromophores are generally higher than those found for the ruthenium(II) tris(diimine) systems, and the directionality of the charge transfer is more certain. The first platinum diimine bis(arylacetylide) triad, constructed by attaching phenothiazene donors to the arylacetylide ligands and a nitrophenyl acceptor to 5-ethynylphenanthroline of the chromophore, exhibited a charge-separated state of 75-ns duration. The first Pt(tpy)(arylacetylide)+-based triad contains a trimethoxybenzamide donor and a pyridinium acceptor and has been structurally characterized. The triad has an edge-to-edge separation between donor and acceptor fragments of 27.95 Angstroms. However, while quenching of the emission is complete for this system, transient absorption (TA) studies reveal that charge transfer does not move onto the pyridinium acceptor. A new set of triads described in detail here and having the formula [Pt(NO2phtpy)(p-C triple-bond C-C6H4CH2(PTZ-R)](PF6), where NO2phtpy = 4'-{4-[2-(4-nitrophenyl)vinyl]phenyl}-2,2';6',2'-terpyridine and PTZ = phenothiazine with R = H, OMe, possess an unsaturated linkage between the chromophore and a nitrophenyl acceptor. While the parent chromophore [Pt(ttpy)(C triple-bond CC6H5)]PF6 is brightly luminescent in a fluid solution at 298 K, the triads exhibit complete quenching of the emission, as do the related donor-chromophore (D-C) dyads. Electrochemically, the triads and D-C dyads exhibit a quasi-reversible oxidation wave corresponding to the PTZ ligand, while the R = H triad and related C-A dyad display a facile quasi-reversible reduction assignable to the acceptor. TA spectroscopy shows that one of the triads possesses a long-lived charge-separated state of approximately 230 ns.     

Numerical Investigation of Graphene as a Back Surface Field Layer on the Performance of Cadmium Telluride Solar Cell

This paper numerically explores the possibility of ultrathin layering and high efficiency of graphene as a back surface field (BSF) based on a CdTe solar cell by Personal computer one-dimensional (PC1D) simulation. CdTe solar cells have been characterized and studied by varying the carrier lifetime, doping concentration, thickness, and bandgap of the graphene layer. With simulation results, the highest short-circuit current (I_sc = 2.09 A), power conversion efficiency (η = 15%), and quantum efficiency (QE~85%) were achieved at a carrier lifetime of 1 × 10³ μs and a doping concentration of 1 × 10¹⁷ cm⁻³ of graphene as a BSF layer-based CdTe solar cell. The thickness of the graphene BSF layer (1 μm) was proven the ultrathin, optimal, and obtainable for the fabrication of high-performance CdTe solar cells, confirming the suitability of graphene material as a BSF. This simulation confirmed that a CdTe solar cell with the proposed graphene as the BSF layer might be highly efficient with optimized parameters for fabrication.     

Phenothiazine–BODIPY–Fullerene Triads as Photosynthetic Reaction Center Models: Substitution and Solvent Polarity Effects on Photoinduced Charge Separation and Recombination

Novel photosynthetic reaction center model compounds of the type donor₂–donor₁–acceptor, composed of phenothiazine, BF₂‐chelated dipyrromethene (BODIPY), and fullerene, respectively, have been newly synthesized using multistep synthetic methods. X‐ray structures of three of the phenothiazine‐BODIPY intermediate compounds have been solved to visualize the substitution effect caused by the phenothiazine on the BODIPY macrocycle. Optical absorption and emission, computational, and differential pulse voltammetry studies were systematically performed to establish the molecular integrity of the triads. The N‐substituted phenothiazine was found to be easier to oxidize by 60 mV compared to the C‐substituted analogue. The geometry and electronic structures were obtained by B3LYP/6‐31G(dp) calculations (for H, B, N, and O) and B3LYP/6‐31G(df) calculations (for S) in vacuum, followed by a single‐point calculation in benzonitrile utilizing the polarizable continuum model (PCM). The HOMO?1, HOMO, and LUMO were, respectively, on the BODIPY, phenothiazine and fullerene entities, which agreed well with the site of electron transfer determined from electrochemical studies. The energy‐level diagram deduced from these data helped in elucidating the mechanistic details of the photochemical events. Excitation of BODIPY resulted in ultrafast electron transfer to produce PTZ–BODIPY^.+–C₆₀^.?; subsequent hole shift resulted in PTZ^.+–BODIPY–C₆₀^.? charge‐separated species. The return of the charge‐separated species was found to be solvent dependent. In nonpolar solvents the PTZ^.+–BODIPY–C₆₀^.? species populated the ³C₆₀* prior to returning to the ground state, while in polar solvent no such process was observed due to relative positioning of the energy levels. The ¹BODIPY* generated radical ion‐pair in these triads persisted for few nanoseconds due to electron transfer/hole‐shift mechanism.     

Nickel‐Catalyzed α‐Carbonylalkylarylation of Vinylarenes: Expedient Access to γ,γ‐Diarylcarbonyl and Aryltetralone Derivatives

We report a Ni‐catalyzed regioselective α‐carbonylalkylarylation of vinylarenes with α‐halocarbonyl compounds and arylzinc reagents. The reaction works with primary, secondary, and tertiary α‐halocarbonyl molecules, and electronically varied arylzinc reagents. The reaction generates γ,γ‐diarylcarbonyl derivatives with α‐secondary, tertiary, and quaternary carbon centers. The products can be readily converted to aryltetralones, including a precursor to Zoloft, an antidepressant drug.     

Pflanzenchemie

Analytical and Bioanalytical Chemistry -     

The picosecond transient Raman spectra of S1 excited oligophenyls, oxazols and stilbene derivatives

Picosecond time-resolved resonance Raman spectra of electronically excited laser-dye molecules, oligophenyls, oxazols, and stilbene derivatives in solution have been obtained. The spectral profiles of several transients are observed to change on the picosecond timescale.     

Molecular weight control of polyacrylamide with sodium formate as a chain‐transfer agent: Characterization via size exclusion chromatography/multi‐angle laser light scattering and determination of chain‐transfer constant

We discuss the synthesis and characterization of polyacrylamide (PAM) homopolymers with carefully controlled molecular weights (MWs). PAM was synthesized via free‐radical solution polymerization under conditions that yield highly linear polymer with minimal levels of hydrolysis. The MW of the PAM homopolymers was controlled by the addition of sodium formate (NaOOCH) to the polymerization medium as a conventional chain‐transfer agent. MWs and polydispersity indices (PDIs) were determined via size exclusion chromatography/multi‐angle laser light scattering analysis; for polymerizations carried out to high conversion, PAM MWs ranged from 0.23 to 6.19 × 10⁶ g/mol, with most samples having PDI ≈2.0. Zero‐shear intrinsic viscosities of the polymers were determined via low‐shear viscometry in 0.514 M NaCl at 25 °C. Data derived from the polymer characterization were used to determine the chain‐transfer constant to NaOOCH under the given polymerization conditions and to calculate Mark–Houwink–Sakurada K and a values for PAM in 0.514 M NaCl at 25 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 560–568, 2003     

An investigation of the changes in the natural frequency of a pile affected by scour

Scour around bridge foundations is one of the leading causes of bridge failure. Up until recently, the monitoring of this phenomenon was primarily based around using underwater instrumentation to monitor the progression of scour holes as they develop around foundation systems. Vibration-based damage detection techniques have been used to detect damage in bridge beams. The application of these vibration based methods to the detection of scour has come to the fore in research in recent years. This paper examines the effect that scour has on the frequency response of a driven pile foundation system, similar to those used to support road and rail bridges. The effect of scour on the vibration characteristics of the pile is examined using laboratory and field testing. It is clear that there is a very clear reduction in the natural frequency of the pile as the severity of scour increases. It is shown that by combining state-of-the-art geotechnical techniques with relatively simple finite element modelling approaches, it is possible to accurately predict the natural frequency of the pile for a given scour depth. Therefore, the paper proposes a method that would allow the estimation of scour depth for a given observed pile frequency.     

A new universal GPC calibration method

A model of GPC separation phenomenon with a new calibration method has been developed based on the probability of molecular size exclusion from a porous packing material. The model was shown to give a theoretical explanation of instrument range and sensitivity. With data from the literature, the new calibration method was shown to be statistically superior to the standard method suggested by Grubisic.