Time-dependent density functional theory investigations on structural modification in carbazole-based organic photosensitizers to improve electron injection in dye-sensitized solar cell

The time-dependent density functional theory approach, implemented at hybrid-B3LYP, GGA-PBE, and density functional-based tight binding levels of theory, was used to model photoinjection in organic dye/TiO₂ quantum dot to explore the prospects of improvement of dye-sensitized solar cell (DSSC). The photosensitizer used in this study consisted of six carbazole-based organic dyes, a cyanoacrylic acid group as an acceptor and an oligothiophene π-bridge spacer. The modifications were made in the dyes by increasing the length of the spacer by adding thiophene and oxadiazole rings at different positions of the donor-acceptor bridge. The structural variations appeared to alter the electronic and optical properties of dyes studied via energy levels and excitation spectra. The UV-Vis spectra calculated for all the dyes in solvents exhibited a red shift in spectral peaks with an increase in the polarity of the solvents. The findings of the study pointed toward the indirect photoinjection of the dye-(TiO₂)₉₆ complex for six different dyes. The substitution of the oxadiazole ring at the center and addition of a thiophene ring at the edge of the spacer produced two dyes that exhibited the lowest injection energies of 0.11 and 0.17 eV, along with the regeneration energies of 1.18 and 1.12 eV, respectively. The dyes reported here may have promising applications in photoanode for enhancing the performance of DSSC.     

Projective synchronization of time‒delayed chaotic systems with unknown parameters using adaptive control method

The present article aims to study the projective synchronization between two identical and non?identical time?delayed chaotic systems with fully unknown parameters. Here the asymptotical and global synchronization are achieved by means of adaptive control approach based on Lyapunov–Krasovskii functional theory. The proposed technique is successfully applied to investigate the projective synchronization for the pairs of time?delayed chaotic systems amongst advanced Lorenz system as drive system with multiple delay Rössler system and time?delayed Chua's oscillator as response system. An adaptive controller and parameter update laws for unknown parameters are designed so that the drive system is controlled to be the response system. Numerical simulation results, depicted graphically, are carried out using Runge–Kutta Method for delay?differential equations, showing that the design of controller and the adaptive parameter laws are very effective and reliable and can be applied for synchronization of time?delayed chaotic systems. Copyright © 2014 John Wiley & Sons, Ltd.     

A New Organic-Paradodecatungstate Hybrid Compound: Synthesis, Characterization and Crystal Structure

An organic–inorganic hybrid compound Na₂(HAn)₈[H₂W₁₂O₄₂]·16H₂O (HAn: p-anisidinium, C₇H₁₀NO) has been synthesized under soft acidic conditions and characterized by infrared and UV–visible spectroscopies, thermogravimetric analysis, cyclic voltammetry and single crystal X-ray diffraction. The compound crystallizes in the monoclinic P2₁/n space group with a = 10.1920(4) Å, b = 34.2901(9) Å, c = 14.0745(5) Å, β = 95.830(3)°, V = 4,893.4(3) Å³ and Z = 4. The compound exhibits a 2D supramolecular structure formed by alternated [paradodecatungstate/Na] and p-anisidinium layers. The catalytic activity of the compound for oxidation of cyclooctene with H₂O₂ was proved and gives rise to good reaction yield.     

Dirhodium(II) Compounds with Bridging Thienylphosphines: Studies on Reversible P,C/P,S Coordination

Monocyclometalated compound [Rh₂{(C₈H₄S)P(C₈H₅S)₂}(CH₃CO₂H)₂(O₂CCH₃)₃] ( 1 a ) and bis‐cyclometalated compound [Rh₂{(C₈H₄S)P(C₈H₅S)₂}₂(CH₃CO₂H)₂(O₂CCH₃)₂] ( 2 a ) have been isolated from the reaction of dirhodium tetraacetate and tris(2‐benzo[b]thienyl)phosphine ( 2 BTP ) using low acidic solutions. By contrast, in pure acetic acid the reaction of Rh₂(O₂CCH₃)₄ with 2 BTP and tris(2‐thienyl)phosphine ( 2 TP ), followed by replacement of the axial acetate ligands by chlorides, led to [Rh₂{(2‐C₈H₅ S )P(2‐C₈H₅S)₂}₂Cl₂(O₂CCH₃)₂] ( 3 b ) and [Rh₂{(2‐C₄H₃ S )P(C₄H₃S)₂}₂Cl₂(O₂CCH₃)₂] ( 5 b ), respectively. These new dirhodium(II) compounds possess equatorial bridging ligands in a phosphorous–sulfur (P,S) coordination mode. The reversible switching between the P,C and P,S bonding mode of the phosphine has been studied in the monocyclometalated [Rh₂{(C₄H₂S)P(C₄H₃S)₂}(CH₃CO₂H)₂(O₂CCH₃)₃] ( 6 a ), which was selectively transformed into compound [Rh₂{(2‐C₄H₃ S )P(C₄H₃S)₂}(CF₃SO₃)(CH₃CO₂H)(O₂CCH₃)₃] ( 7 c ) in triflic acid media. Remarkably, compound 7 c reverts to the starting compound 6 a upon treatment with sodium acetate. Theoretical DFT calculations for both the P,C/P,S rearrangement and the base‐promoted reversion have been performed to explain the experimental findings. Data suggest the P,C/P,S rearrangement occurs by means of a “concerted protonation–demetalation mechanism” followed by η² coordination of the thienyl ring and subsequent isomerization to the S‐η¹‐coordination mode. In the reversion reaction, the base coordinated at the axial position would promote a concerted metalation–deprotonation mechanism.     

Fukuyama reduction,Fukuyama coupling and Fukuyama–Mitsunobu alkylation: recent developments and synthetic applications

Fukuyama reaction for the synthesis of multifunctional aldehydes, secondary amines and ketones has gained considerable importance in synthetic organic chemistry because of mild reaction conditions. The use of thioesters in both Fukuyama aldehydes and ketones synthesis is highly attractive for organic chemists as they are easily accessible from corresponding carboxylic acids. Fukuyama–Mitsunobu reaction utilizes 2-nitrobenzenesulfonyl (Ns) for the protection/activation/deprotection of primary amines to afford secondary amines in good yields and high enantioselectivities. This review presents recent synthetic developments and applications of Fukuyama reaction for the synthesis of aldehydes, secondary amines and ketones.

Graphic abstract

     

Growth of Yb3+-doped KY3F10 concentration gradient crystal fiber by laser-heated pedestal growth (LHPG) technique

Crystal fiber of cubic Yb³⁺-doped KY₃F₁₀ has been grown. Both, mono-doped and concentration gradient fibers were grown by laser-heated pedestal growth (LHPG) method under argon atmosphere. The preparation of feed rod materials under CF₄ atmosphere prior to LHPG is efficient to obtain oxygen-free fluorides. Yb³⁺-doped KY₃F₁₀ crystals have excellent spectroscopic properties, weak self-quenching property and can be expected for solid-state laser application.     

Convergence of Point Processes with Weakly Dependent Points

For each n≥1, let {X _j,n }_1≤j≤n be a sequence of strictly stationary random variables. In this article, we give some asymptotic weak dependence conditions for the convergence in distribution of the point process $N_{n}=\sum_{j=1}^{n}\delta_{X_{j,n}}For each n≥1, let {X _j,n }_1≤j≤n be a sequence of strictly stationary random variables. In this article, we give some asymptotic weak dependence conditions for the convergence in distribution of the point process N_n=?_j=1ⁿd_Xj,nN_{n}=\sum_{j=1}^{n}\delta_{X_{j,n}} to an infinitely divisible point process. From the point process convergence we obtain the convergence in distribution of the partial sum sequence S _n =∑ _j=1 ⁿ X _j,n to an infinitely divisible random variable whose Lévy measure is related to the canonical measure of the limiting point process. As examples, we discuss the case of triangular arrays which possess known (row-wise) dependence structures, like the strong mixing property, the association, or the dependence structure of a stochastic volatility model.     

First sonochemical,simple and solvent-free synthesis of chiral tert-butanesulfinimines using silica supported p-toluenesulfonic acid

A solvent-free, versatile procedure has been developed for the effective synthesis of tert-butanesulfinylimines of a variety of aldehydes using chiral tert-butanesulfinamides under green, sonochemical conditions. This method utilizes silica supported p-toluenesulfonic acid (pTSA·SiO₂) as an efficient, safer and inexpensive catalyst under aerobic conditions. The practicable simplicity, easy preparation of the catalyst from readily available substances, high substrate scope, excellent yields of products in short reaction times and environmentally benign (solvent-free sonochemical) conditions are the exceptional assets of this finding.     

Hölder Continuity of the Rotation Number for Quasi-Periodic Co-Cycles in $${SL(2, \mathbb R)}$$

We prove two results on the rotation number of the skew-product system \({(\omega ,A):(\theta ,y)\in\mathbb T^d\times\mathbb R^2\mapsto (\theta +\omega ,A(\theta)y)\in\mathbb T^d\times\mathbb R^2,}\) where ω is Diophantine and \({A(\theta)\in SL(2, \mathbb R)}\) is homotopic to the identity. On the one hand, we prove that this function has the behavior of a \({\frac{1}{2}-}\) Hölder function. On the other, we show that the length of the gaps has a sub-exponential estimate which depends on its label given by the gap-labeling theorem. We give also an estimate of the complement of the spectrum. These results are obtained by studying the reducibility of the quasi-periodic co-cycle (ω , A).