Catalytic aromatic C–H bond activation and functionalization to useful molecules is highly important in chemical synthesis. This study introduces a novel use of the popular N-heterocyclic carbenes (NHC), for first-time, rhodium(III)-catalyzed cascade double activation–annulation, within backbone readily available imidazolium substrates synthesize variety nicely decorated polycyclic heteroaromatic containing benzo[ij]imidazo[2,1,5-de]quinolizinium architectures which might be developing new...

Developing efficient H2-evolution artificial electrocatalysts often takes inspiration from the active sites of [FeFe]/[NiFe]-hydrogenases to incorporate smartly designed amine/thiolato-based proton-shuttle motifs. Interestingly, [Fe]-hydrogenase (the third type hydrogenases) consists an Fe-bound adjacent pyridinol/pyridinone proton shuttle, which assists in reversible heterolytic H2-cleavage during its operation. However, so far, this functionality has not been exploited develop...

The first example of a hitherto-unknown facet catalytic photooxidant capability nitrenium cations is reported herein. fundamental limitation inability the traditional and nitreniums to achieve excited-state redox potential beyond +2.0 V (vs Ag/AgCl), primary requirement for powerful photooxidant, addressed in this work by developing structurally unique class N-fused cations, with required structural engineering involving extensive π-conjugation through ring fusion at site, which enabled...

The highly active Friedel-Crafts alkylation (FCA) catalyst, [Ir(COD)Cl(SnCl3)(SnCl4)(arene)]+Cl- (1-SnCl4), is easily generated in one-pot from [Ir(COD)Cl]2 or [Ir(COD)(mu-Cl)Cl(SnCl3)]2 (1) and SnCl4. reaction of arenes, heteroarenes with benzyl, allyl alcohols promoted by 1-SnCl4 (1 mol %) high turnover frequency. Kinetic evidence presented to establish FCA pattern. From dual-catalyst combination studies varying the transition metal main group partner, efficiency present catalysts...

Reactions of arenes and heteroarenes with aromatic aldehydes proceeded smoothly in the presence a catalytic combination [Ir(COD)Cl]2−SnCl4 to afford corresponding triarylmethane derivatives (TRAMs) high yields. This 100% TRAM selective transformation is clean eliminates use acid systems.

Flip-flopping away: Multivalue random access memory can be achieved using electrically addressable Os2+-based multilayers. The controllable optical properties of the multilayers allow construction devices that are able to store up five different states depend on given electrical inputs (see picture). functions represented by sequential logic circuits equivalent flip-flop and flip-flap-flop devices.

Organic molecules containing imidazolium and pyridine backbone are of special interest in many branches chemistry, therefore, overcoming the scarcity their catalytic functionalization protocol leading to structurally important derivatives is strongly desired. This study demonstrates an unprecedented bimodal C–H activation–functionalization catalysis on such organic which contain motif (potential N-heterocyclic carbene donor) chelating fashion difficult functionalize by trivial activation...

Disclosed herein is the unique conjugative role of N-heterocyclic carbene (NHC) ligands as a directing group in aromatic C-H activation, coupled with facile NHC-alkenyl annulative reductive elimination which guided Rh(III)-catalyzed intermolecular annulations imidazolium salts and alkynes under ambient conditions leading to structurally important imidazo[1,2-a]quinolinium motifs.

Catalytic conversion of CO2 via "transfer hydrogenation" using renewable non-H2 compounds (such as biomass-derived (poly)alcohols) to produce valuable energy-relevant chemicals, is a promising alternative strategy the traditionally employed "hydrogenation" with gaseous H2. However, CO2-transfer hydrogenation has been explored exceptionally less, and limited but encouraging success achieved in recent time by applying high pressure (up 50 atm) gas. For safe simple operation, ambient-pressure...

Biomimetic NAD(P)H-type organic hydride donors have recently been advocated as potential candidates to act metal-free catalysts for fuel-forming reactions such the reduction of CO2 formic acid and methanol, similar natural photosynthesis process fixing into carbohydrates. Although these artificial synthetic hydrides are extensively used in chemistry a stoichiometric manner, translating them has challenging due problems associated with regeneration species under applied reaction conditions. A...

Here we report the first use of self-propagating molecule-based assemblies (SPMAs) as efficient electron-transporting layers for inverted organic photovoltaic (OPV) cells. P3HT-PCBM cells functionalized with optimized SPMAs exhibit power conversion efficiencies approaching 3.6% (open circuit voltage = 0.6 V) vs 1.5% and 2.4% bare ITO Cs(2)CO(3)-coated devices, respectively. The dependence cell response parameters on interlayer thickness is investigated, providing insight into how to further...

Abstract Disclosed here is a molecular switch which responds to acid‐base stimuli and serves as bi‐state catalyst for two different reactions. The states of the serve highly active poorly catalytic reactions (namely hydrogenation dehydrogenative coupling) but in complementary manner. system was used an assisted tandem catalysis set‐up involving coupling amine then resulting imine product by switching between respective catalyst.

A molecular coordination-switch controlled by acid–base input has been developed and utilized in switchable catalysis. The switch consists of a hybrid pyridylidene–benzimidazole ligand bound to an IrIIICp* moiety wherein the benzimidazole functionality for acid/base reversible coordination, switching between IrIII-benzimidazole species (form I; neutral imino-type N-coordination) IrIII-benzimidazolate II; anionic amido-type N–Ir bonding). Owing distinctly different nature metal–ligand...

Recently, Mn-catalyzed hydrogenation reactions have gained significant interest due to their importance in various challenging transformations. Among several classes of organic substrates, including amides, ketones, carbamates, urea-derivatives, (cyclic) carbonates/polycarbonates, CO2, and CO2 derivatives, N-heteroarene using a Mn-based system is severely underdeveloped. Only handful reports are known the literature, which mainly use expensive phosphine-based ligand systems for designing...

Generation of clean energy in a viable manner demands efficient and sustainable catalysts. One prospective method generation is the electrochemical hydrogen evolution reaction (HER). Over years, various transition metal-based complexes/polymeric organic materials were utilized HER. However, use redox-active small molecule as catalyst for HER has not been explored well. The requirements strongly acidic solution, very high overpotential, stability under conditions pose several challenges...

A highly efficient secondary benzylation procedure has been demonstrated using a high-valent heterobimetallic complex [Ir2(COD)2(SnCl3)2(Cl)2(μ-Cl)2] 1 as the catalyst in 1,2-dichloroethane to afford corresponding benzylated products moderate excellent yields. The reaction was performed not only with carbon nucleophiles (arenes and heteroarenes) but also oxygen (alcohol), nitrogen (amide sulfonamide), sulfur (thiol) nucleophiles. Mechanistic investigation showed intermediacy of ether this...

Here we present the critical role of molecular structure and reaction parameters on nature thin-film growth, using a versatile two-step assembly method with organic metal-organic chromophores cross-linked palladium. It was found that polypyridyl complexes exhibit exponential whereas, under identical conditions, systems linear behavior. The internal film morphology plays pivotal in storage usage palladium, where more porous results growth. Interestingly, through proper tuning growth...

Just two steps: Two new strategies with regard to the "methanol economy" proposal have been developed: an indirect CO2-derivative-to-methanol conversion by means of a metal ligand cooperative catalysis and stepwise CO2-to-methanol via cascade catalysis. These represent significant scientific development respect current on-going challenges on energy fuel for sustainable future.

A new rhodium(III)-catalyzed protocol for C–H activation and functionalization of poorly reactive pyridine backbones with the aid in-built N-heterocyclic carbene ligand has been presented. Mechanistic investigations including isolation single crystal X-ray structural characterization pre- postfunctionalized rhodium(III)-intermediates suggested a plausible pyridine-coordination effect in present NHC-directed cyclometalative annulation C(3)–H bond rings internal alkynes. The strategy enables...

Abstract This work discloses that a simple change in the anion of copper(II) reagent along with reaction solvent can dramatically alter course Cp*Rh III ‐catalyzed C−H activation–annulation leading to completely switchable chemoselective products. The nature terms its coordinating ability and basicity, also polarity have been found be crucial factors observed divergence.

Disclosed herein is a rhodium(iii)-catalyzed novel one-step back-to-back double rollover annulation on pyridine and pyrazine backbones leading to structurally optoelectronically diverse class of nicely decorated multi-ring-fused, extensively π-conjugated, N-enriched PAH molecules by virtue orchestrated quadruple C-H activation events. Selected N-PAHs have been utilized as potential mitochondria lysosome markers.