Silica-Supported MnII Sites as Efficient Catalysts for Carbonyl Hydroboration,Hydrosilylation, and Transesterification

Manganese, the third most abundant transition-metal element after iron and titanium, has recently been demonstrated to be an effective homogeneous catalyst in numerous reactions. Herein, the preparation of silica-supported Mn^II sites is reported using Surface Organometallic Chemistry (SOMC), combined with tailored thermolytic molecular precursors approach based on Mn₂[OSi(OtBu)₃]₄ and Mn{N(SiMe₃)₂}₂⋅THF. These supported Mn^II sites, free of organic ligands, efficiently catalyze numerous reactions: hydroboration and hydrosilylation of ketones and aldehydes as well as the transesterification of industrially relevant substrates.     

Self‐emulsion polymerization of amphiphilic monomers—a green route to synthesis of polymeric nanoscaffolds

Self‐emulsion polymerization (SEP), a green route developed by us for the polymerization of amphiphilic monomers, does not require any emulsifier or an organic solvent except that the water‐soluble initiators such as 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane]dihydrochloride (VA‐044) and potassium persulfate (KPS) are only used. We report here the polymer nanoscaffolds from a number of amphiphilic monomers, which can be used for in situ encapsulation of a variety of nanoparticles. As a demonstration of the efficacy of these nanoscaffolds, the synthesis of a biocompatible hybrid nanoparticle (nanohybrid), prepared by encapsulating Fe₃O₄ magnetic nanoparticle (Fe₃O₄ MNPs) in poly(2‐hydroxyethyl methacrylate) in water, for MRI application is presented. The nanohybrid prepared following the SEP in the form of an emulsion does not involve the use of any stabilizing agent, crosslinker, polymeric emulsifier, or surfactant. This water‐soluble, spherical, and stable nanohybrid containing Fe₃O₄ MNPs of average size 10 ± 2 nm has a zeta potential value of ?41.89 mV under physiological conditions. Magnetic measurement confirmed that the nanohybrid shows typical magnetic behavior having a saturation magnetization (Ms) value of 32.3 emu/g and a transverse relaxivity (r2) value of 29.97 mM^?1 s^?1, which signifies that it can be used as a T2 contrast agent in MRI. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

Multi-targeted molecular docking,drug-likeness and ADMET studies of derivatives of few quinoline- and acridine-based FDA-approved drugs for anti-breast cancer activity

Structural Chemistry - Quinoline- and acridine-based drugs are widely used as anti-breast cancer agents. These drugs act through various mechanisms of action; for example, neratinib acts on...     

Boron(iii) β-diketonate-based small molecules for functional non-fullerene polymer solar cells and organic resistive memory devices

A class of acceptor–donor–acceptor chromophoric small-molecule non-fullerene acceptors, 1–4, with difluoroboron(iii) β-diketonate (BF₂bdk) as the electron-accepting moiety has been developed. Through the variation of the central donor unit and the modification on the peripheral substituents of the terminal BF₂bdk acceptor unit, their photophysical and electrochemical properties have been systematically studied. Taking advantage of their low-lying lowest unoccupied molecular orbital energy levels (from −3.65 to −3.72 eV) and relatively high electron mobility (7.49 × 10⁻⁴ cm² V⁻¹ s⁻¹), these BF₂bdk-based compounds have been employed as non-fullerene acceptors in organic solar cells with maximum power conversion efficiencies of up to 4.31%. Moreover, bistable resistive memory characteristics with charge-trapping mechanisms have been demonstrated in these BF₂bdk-based compounds. This work not only demonstrates for the first time the use of a boron(iii) β-diketonate unit in constructing non-fullerene acceptors, but also provides more insights into designing organic materials with multi-functional properties.

Boron(iii) β-diketonates have been demonstrated to serve as multi-functional materials in NFA-based OPVs and organic resistive memories.     

Highly Phosphorescent Crystals of Square‐Planar Platinum Complexes with Chiral Organometallic Linkers: Homochiral versus Heterochiral Arrangements,Induced Circular Dichroism,and TD‐DFT Calculations

A novel class of chiral luminescent square‐planar platinum complexes with a π‐bonded chiral thioquinonoid ligand is described. Remarkably the presence of this chiral organometallic ligand controls the aggregation of this square planar luminophor and imposes a homo‐ or hetero‐chiral arrangement at the supramolecular level, displaying non‐covalent Pt–Pt and π–π interactions. Interestingly these complexes are highly luminescent in the crystalline state and their photophysical properties can be traced to their aggregation in the solid state. A TD‐DFT calculation is obtained to rationalize this unique behavior.     

Tuning of Supramolecular Architectures of l‐Valine‐Containing Dicyanoplatinum(II) 2,2′‐Bipyridine Complexes by Metal–Metal, π–π Stacking,and Hydrogen‐Bonding Interactions

A series of newly synthesized dicyanoplatinum(II) 2,2′‐bipyridine complexes exhibits self‐assembly properties in solution after the incorporation of the l ‐valine amino units appended with various hydrophobic motifs. These l ‐valine‐derived substituents were found to have critical control over the aggregation behaviors of the complexes in the solution state. On one hand, one of the complexes was found to exhibit interesting circularly polarized luminescence (CPL) signals at low temperature due to the formation of chiral spherical aggregates in the temperature‐dependent studies. On the other hand, systematic transformation from less uniform aggregates to well‐defined fibrous and rod‐like structures via Pt???Pt and π–π stacking interactions has also been observed in the mixed‐solvent studies. These changes were monitored by UV/Vis absorption, emission, circular dichroism (CD), and CPL spectroscopies, and morphologies were studied by electron microscopy.     

Air‐Stable Spirofluorene‐Containing Ladder‐Type Bis(alkynyl)borane Compounds with Readily Tunable Full Color Emission Properties

A series of air‐stable spiro‐fused ladder‐type boron(III) compounds has been designed, synthesized, and the electrochemistry and photophysical behavior have been characterized. By simply varying the substituents on the pyridine ring and extending the π‐conjugation of the spiro framework, the emission color of these compounds can be easily fine‐tuned spanning the visible spectrum from blue to red. All compounds exhibit a broad and structureless emission band across the entire visible region, assigned as an intramolecular charge‐transfer transition originating from the thiophene of the spiro framework to the pyridine‐borane moieties. In addition, these compounds demonstrate high photoluminescence quantum yields of up to 0.81 in dichloromethane solution and 0.86 in doped thin films. Some of the compounds have also been employed as emissive materials, in which solution‐processed organic light‐emitting devices (OLEDs) with tunable emission colors spanning the visible spectrum from blue, green to red have been realized, demonstrating the potential applications of these boron compounds in OLEDs.