Organic dyes containing thienylfluorene conjugation for solar cells

New organic dyes that contain variable lengths of conjugation featuring alternating thiophene and fluorene segments have been synthesized and efficient nano-crystalline TiO2 based dye-sensitized solar cells were fabricated using these molecules as light-harvesting sensitizers.     

Organic dyes incorporating low-band-gap chromophores for dye-sensitized solar cells

Versatile dyes based on benzothiadiazole and benzoselenadiazole chromophores have been developed that perform efficiently in dye-sensitized solar cells. Power conversion efficiency of 3.77% is realized for a dye in which charge recombination is probably hindered by the nonplanar charge-separated structure.     

Synthesis of conjugated organic dyes containing alkyl substituted thiophene for solar cell

Three organic dyes, JK-41, JK-42, and JK-43 containing bis-dimethylfluoreneaniline and alkyl substituted thiophene unit are designed and synthesized. Under standard global AM 1.5 solar condition, the JK-41 sensitized cell gave a short circuit photocurrent density (J_sc) of 15.23 mA cm⁻², open circuit voltage (V_oc) of 0.67 V, and a fill factor of 0.67, corresponding to an overall conversion efficiency η of 7.69%. Molecular-orbital calculations of the three dyes suggest that the electron distribution moves from the aniline derivative to the cyanoacrylic acid moiety. We found that the power conversion efficiency was shown to be quite sensitive to the structural variations of alkyl substituted thiophene moiety.     

Organic dyes containing a coplanar indacenodithiophene bridge for high-performance dye-sensitized solar cells

A series of new organic dyes exploiting coplanar indacenodithiophene as the central π-spacer of the classical donor-(π-spacer)-acceptor configuration were synthesized and characterized for dye-sensitized solar cells. The coplanarity of the indacenodithiophene core facilitates efficient donor to acceptor charge transfer, imparting the new organic dyes significant bathochromic shifts and remarkable power conversion efficiencies of up to 6.7% (DTInDT) under AM 1.5G radiation.     

Organic dyes with a novel anchoring group for dye-sensitized solar cell applications

Two novel trialkylsilyl-containing organic sensitizers (JK-53 and JK-54) have been designed and synthesized. Nanocrystalline TiO₂–silica-based dye-sensitized solar cells (DSSCs) were fabricated using these dyes. Under standard global AM 1.5 solar conditions, the JK-53-sensitized cell gave a short-circuit photocurrent density (J_sc) of 6.37 mA cm^?2, an open-circuit voltage (V_oc) of 0.70 V, and a fill factor of 0.74. These values correspond to an overall conversion efficiency (η) of 3.31%. By comparison, the JK-54-sensitized cell resulted in a J_sc of 7.52 mA cm^?2, a V_oc of 0.71 V, and a fill factor of 0.75. These values give an overall conversion efficiency of 4.01%.     

Organic dyes containing nonsubstituted aryl amino moieties and azobenzene units for dye‐sensitized solar cells

A series of novel sensitizers were successfully synthesized utilizing azobenzene as a π‐linkage unit for the D–π–A structure. A slight red shift on the absorption spectra and λ_onset of the sensitizers could be observed when the thienyl group was introduced to the acceptor moiety (A). In addition, replacing the donor moiety (D) from carbazole to diarylamino could lead to a negative shift (approximately 0.3 V) in the first oxidation potential. DFT calculation was also carried out and the trend of calculated HOMO–LUMO gaps was consistent to the experimental data obtained from the CV results ( DT1 < DT2 < DT3 < DT4 ). These sensitizers were then employed in dye‐sensitized solar cells to investigate their photovoltaic performances. Highest power conversion efficiency (PCE) of 0.84% was achieved for DT1 ‐based DSSC according to its most bathochromic absorption spectrum.     

Tautomerism of pyrimidine bases—uracil,cytosine, isocytosine: Theoretical study with complete optimization of geometry

The semiempirical MINDO /3 method with complete optimization of geometry is employed to calculate the electronic ground-state properties (dipole moments and ionization potentials) and the energies of various tautomeric forms of uracil, uracil monoanion, cytosine, and isocytosine. The results are shown to be consistent with most of the experimental data. Accuracy of various quantum–mechanical methods is discussed. Particular attention is paid to the influence of the geometry optimization on energy differences between various tautomers. Some qualitative conclusions of biological importance are drawn from these calculations.     

Interaction of electron acceptors with bases—XVI Proton magnetic resonance spectra of Meisenheimer compounds

PMR spectra of several Meisenheimer compounds have been measured in various solvents. Evidence is given that in such products derived from 1,3,5-trinitrobenzene the alkoxy group is readily exchanged in solvolysis by the acetonyl group. Products formed in solution by various concentrations of methoxide on several different polynitroaromatics have also been studied.     

1,2-dihydroisoquinolines—XIX: Rearrangement V

1-Allyl-2, 3-dimethyl-1, 2-dihydroisoquinoline does not rearrange to 3-allyl-2, 3-dimethyl-3, 4-dihydroisoquinolinium chloride when treated with dilute hydrochloric acid, but the introduction of a C₁-Me or a C₆-OMe substituent enables a reaction to proceed. A rationalisation is provided for these observations.     

Organic dyes incorporating the benzo[1,2-b:4,5-b']dithiophene moiety for efficient dye-sensitized solar cells

A new class of organic sensitizers incorporating a benzo[1,2-b:4,5-b']dithiophene (BDT) unit as conjugated spacer has been synthesized and successfully used for dye-sensitized solar cells (DSSCs). The length of the π-conjugated spacers has a strong impact on electro-optical properties of these dyes, leading to the conversion efficiencies ranging from 4.17 to 5.68% under AM 1.5 G irradiation. This result indicates that the BDT unit is a promising candidate in organic sensitizers.     

Metal-free organic dyes for dye-sensitized solar cells: recent advances

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A conversational mass spectral search and retrieval system—II: Combined search options

An interactive, conversational mass spectral search system based on 8782 uncertified electron-impact mass spectra and accessible over ordinary telephone lines, is described. Compounds whose mass spectra are in the file can be immediately identified and very useful structural inferences can be obtained for compounds that are not represented in the file. The file may be searched in a number of ways, including by peaks and intensities, molecular weight, complete and partial molecular formula, molecular weight plus peaks/intensities, molecular formula plus peaks/intensities and molecular weight plus molecular formula. Lastly, the complete spectrum of any compound in the file can be printed out.     

Nature-driven photochemistry for catalytic solar hydrogen production: a Photosystem I-transition metal catalyst hybrid

Solar energy conversion of water into the environmentally clean fuel hydrogen offers one of the best long-term solutions for meeting future energy demands. Nature provides highly evolved, finely tuned molecular machinery for solar energy conversion that exquisitely manages photon capture and conversion processes to drive oxygenic water-splitting and carbon fixation. Herein, we use one of Nature's specialized energy-converters, the Photosystem I (PSI) protein, to drive hydrogen production from a synthetic molecular catalyst comprised of inexpensive, earth-abundant materials. PSI and a cobaloxime catalyst self-assemble, and the resultant complex rapidly produces hydrogen in aqueous solution upon exposure to visible light. This work establishes a strategy for enhancing photosynthetic efficiency for solar fuel production by augmenting natural photosynthetic systems with synthetically tunable abiotic catalysts.     

Design of high‐performance chlorine type dyes for dye‐sensitized solar cells

Intrinsic defect of electronic structure for the chlorine‐type porphyrin 1, which was synthesized for use in dye‐sensitized solar cell (DSSC), is found by theoretical calculation including density functional method (DFT), time‐dependent DFT, and C+/C? function. It is believed that the limited cell performance obtained by using dye 1 as the sensitizer is due to the existence of this electronic defect. To avoid this defect, a series of novel molecules with electron deficient π bridge were designed. The subsequent theoretical calculation indicated that the electron deficient π bridge in the newly designed molecule is quite effective in offsetting the electronic defect observed for dye 1. The parameters for the designed molecules closely associated with open‐circuit voltage and short‐circuit current density including dipole moment of dye vertical to the surface of semiconductor and light‐harvesting efficiency were then evaluated. By comparing these parameters of designed dyes with those of dye 1, we can predict that the DSSC based on dye 4 (2, 6‐cyan benzoic acid as anchoring group) should possess enhanced performance, which would be a valuable theoretical guidance for the practical work. © 2013 Wiley Periodicals, Inc.     

A new N-alkylation reaction—V: NMR investigations

The structure elucidation of some isomeric imidazo(1,2-a)pyrimidones by NMR spectroscopy is described. The tautomerism of the compounds with non-substituted nitrogen is also discussed.     

The interaction of electron acceptors with bases—II The spectrum of s-trinitrobenzene in the presence of ammonia and aliphatic amines

The interaction of s-trinitrobenzene with certain aliphatic amines has been studied spectrophotometrically. It is suggested in solutions in ethanol or chloroform, an adduct is initially formed by a dative bond between the nitrogen of the amine molecule and the 2-position in s-trinitrobenzene. The initial reactions are reversed by acid, but in time further irreversible reactions occur.     

Molecular design of organic dyes with diketopyrrolopyrrole for dye‐sensitized solar cell: A theoretical approach

Three designed metal‐free dyes based on 3‐(10‐butyl‐8‐(methylthio)‐10H‐phenothiazin‐3‐yl)‐2‐cyanoacrylic acid (V5) are investigated by density functional theory (DFT) and time‐dependent DFT to improve the efficiency of V5‐based solar cell devices. We have studied the geometrical structures, excitations, electronic structures, and conduction band shift caused by dye adsorption. The results indicate that the designed dyes have several merits compared with V5 including: (i) smaller energy band gaps and the LUMO closer to conduction band of TiO₂; (ii) wider absorption spectra and higher oscillator strength; (iii) larger dipole moment that lead to higher V_oc value. Our work suggests that the modification of π‐bridge with diketopyrrolopyrrole unit is very effective for designing novel metal‐free dyes with improved performance for dye‐sensitized solar cells (DSSCs). These findings are expected to provide a bright way to design new efficient metal‐free organic DSSCs. © 2014 Wiley Periodicals, Inc.     

ChemInform Abstract: Structural Study of the NaCdVO4—Cd3V2O8 and CdO—V2O5 Sections of the Ternary System Na2O—CdO—V2O5.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

PathOpt—A global transition state search approach: Outline of algorithm

We propose a new algorithm to determine reaction paths and test its capability for Ar₁₂ and Ar₁₃ clusters. Its main ingredient is a search for the local minima on a (n?1) dimensional hyperplane (n = dimension of the complete system in Cartesian coordinates) lying perpendicular to the straight line connection between initial and final states. These minima are part of possible reaction paths and are, hence, used as starting points for an uphill search to the next transition state. First, path fragments are obtained from subsequent relaxations starting from these transition states. They can be combined with information from the straight line connection procedure to obtain complete paths. Our test computations for Ar₁₂ and Ar₁₃ clusters prove that PathOpt delivers several reaction paths in one round. © 2013 Wiley Periodicals, Inc.