Reactions in Water - A Greener Approach Using Ruthenium Catalysts.

Reactions using transition metals as catalysts have emerged as an efficient method in the recent times. However, the selection of solvent plays a crucial role in this regard. Several solvents used traditionally suffer majorly with problems of toxicity; high boiling point etc. leading to drastic reaction conditions. Water being a non-toxic, non-inflammable and environmentally benign can replace the hazardous organic solvents in laboratory as well as industry. Maintaining a minimum catalyst loading percentage we can advantageously avail high levels of selectivity. Water was found to be a good solvent medium for several metal catalysed reactions. An intramolecular deprotonation mechanism is followed by the ruthenium (II) catalysts in water; thereby, facilitating the catalytic action of the metal. These studies can help the industrial chemists to utilize water as a solvent for their reactions towards improvement of their waste management procedure. This review mainly focuses on the several recent developments in the above direction.

Effect of Electron-Withdrawing Chlorine Substituent on Morphological and Photovoltaic Properties of All Chlorinated D-A-Type Quinoxaline-Based Polymers.

The choice of the chlorine (Cl) atom as an electron-withdrawing substituent in conjugated polymers leads to a higher potential in the commercialization of polymer solar cells than its fluorine counterpart because of the versatility and cost-effectiveness of the chlorination process. In addition, the population and location of Cl substituents can significantly influence the photovoltaic characteristics of polymers. In this study, three chlorinated quinoxaline-based polymers were invented to examine the numerical and positioning effects of the Cl atom on their photovoltaic characteristics. The number of Cl substituents in the reference polymer, PBCl-Qx, was adjusted to three: two Cl atoms in the benzodithiophene-type D unit and one Cl atom in the quinoxaline-type A unit. Subsequently, two more Cl atoms were selectively introduced at the 4- and 5-positions of the alkylated thiophene moieties at the 2,3-positions of the quinoxaline moiety in PBCl-Qx to obtain the additional polymers PBCl-Qx4Cl and PBCl-Qx5Cl, respectively. The conventional PBCl-Qx4Cl device exhibited a better power conversion efficiency (PCE) of 12.95% as compared to those of PBCl-Qx (12.44%) and PBCl-Qx5Cl (11.82%) devices. The highest PCE of the device with PBCl-Qx4Cl was ascribed to an enhancement in the open-circuit voltage and fill factor induced by the deeper energy level of the highest occupied molecular orbital and the favorable morphological features in its blended film with Y6.

Effect of electron-withdrawing fluorine and cyano substituents on photovoltaic properties of two-dimensional quinoxaline-based polymers.

In this study, strong electron-withdrawing fluorine (F) and cyano (CN) substituents are selectively incorporated into the quinoxaline unit of two-dimensional (2D) D-A-type polymers to investigate their effects on the photovoltaic properties of the polymers. To construct the 2D polymeric structure, electron-donating benzodithiophene and methoxy-substituted triphenylamine are directly linked to the horizontal and vertical directions of the quinoxaline acceptor, respectively. After analyzing the structural, optical, and electrochemical properties of the resultant F- and CN-substituted polymers, labeled as PBCl-MTQF and PBCl-MTQCN, respectively, inverted-type polymer solar cells with a non-fullerene Y6 acceptor are fabricated to investigate the photovoltaic performances of the polymers. It is discovered that the maximum power conversion efficiency of PBCl-MTQF is 7.48%, whereas that of PBCl-MTQCN is limited to 3.52%. This significantly reduced PCE of the device based on PBCl-MTQCN is ascribed to the formation of irregular, large aggregates in the active layer, which can readily aggravate the charge recombination and charge transport kinetics of the device. Therefore, the photovoltaic performance of 2D quinoxaline-based D-A-type polymers is significantly affected by the type of electron-withdrawing substituent.

Solvent Engineering of Colloidal Quantum Dot Inks for Scalable Fabrication of Photovoltaics.

Development of colloidal quantum dot (CQD) inks enables single-step spin-coating of compact CQD films of appropriate thickness, enabling the promising performance of CQD photovoltaics (CQDPVs). Today's highest-performing CQD inks rely on volatile n-butylamine (BTA), but it is incompatible with scalable deposition methods since a rapid solvent evaporation results in irregular film thickness with an uneven surface. Here, we present a hybrid solvent system, consisting of BTA and N,N-dimethylformamide, which has a favorable acidity for colloidal stability as well as an appropriate vapor pressure, enabling a stable CQD ink that can be used to fabricate homogeneous, large-area CQD films via spray-coating. CQDPVs fabricated with the CQD ink exhibit suppressed charge recombination as well as fast charge extraction compared with conventional CQD ink-based PVs, achieving an improved power conversion efficiency (PCE) of 12.22% in spin-coated devices and the highest ever reported PCE of 8.84% among spray-coated CQDPVs.

Access to small molecule semiconductors via C-H activation for photovoltaic applications.

The first methodology of ruthenium carboxylate-catalysed single step oxidative cross coupling that challenges the conventional Stille and Suzuki coupling reactions, affording BT and MFBT derivatives in the absence of protecting groups, was developed. Both mono and bi-arylated derivatives are formed in moderate to high yields (30-75%). Innately high selectivity, low catalyst loading and lack of formation of regio-isomers ensure the large-scale synthesis of various photonic and electronic materials employing this method.

Nitrite reduction mediated by the complex RuIII(EDTA).

Reported is the first example of a ruthenium(III)-complex, Ru(III)(EDTA) (EDTA(4-) = ethylenediaminetetraacetate), that mediates O-atom transfer from nitrite to the biological thiols cysteine and glutathione, leading to the formation of [Ru(III)(EDTA)(NO(+))](0). However, at pH below 5.0, the coordinated nitrite ion in the [Ru(III)(EDTA)(NO2)](2-) complex undergoes proton-assisted decomposition, resulting in the formation of a [Ru(III)(EDTA)(NO(+))](0) species.