In-Cage Recombination Facilitates the Enantioselective Organocatalytic [1,2]-Rearrangement of Allylic Ammonium Ylides.

The [1,2]-rearrangement of allylic ammonium ylides is traditionally observed as a competitive minor pathway alongside the thermally allowed [2,3]-sigmatropic rearrangement. Concerted [1,2]-rearrangements are formally forbidden, with these processes believed to proceed through homolytic C-N bond fission of the ylide, followed by radical-radical recombination. The challenges associated with developing a catalytic enantioselective [1,2]-rearrangement of allylic ammonium ylides therefore lie in biasing the reaction pathway to favor the [1,2]-reaction product, alongside controlling a stereoselective radical-radical recombination event.

Highly Conductive Non-Calcined 2D CuCo Bimetallic-Organic Framework for Urea Electrolysis in Simulated Seawater.

Global clean energy demands can be effectively addressed using the promising approach of hydrogen energy generation combined with less energy consumption. Hydrogen can be generated, and urea-rich wastewater pollution can be mitigated in a low-energy manner using the urea oxidation reaction (UOR). This paper seeks to assemble a unique electrocatalyst of a pristine 2D MOF, [Co(HBTC)(DMF)] (Co-MUM-3), from 1,3,5-benzenetricarboxylate (BTC) to oxidize urea in simulated seawater.

Integration of Open Metal Sites in an Amino-Functionalized Sm(III)-Organic Framework toward Enhanced Third-Order Nonlinear Optical Property.

A variety of new inorganic and organic materials have emerged to advance laser technologies and optical engineering. A rational design approach can contribute significantly to fabricating nonlinear optically active metal-organic frameworks (MOFs) by considering the underlying structure-property linkage. Here, it has been embarked on a study of novel samarium(III) MOF, ([Sm(ata)(DMF)]·DMF (ata: 2-aminoterephthalate), abbreviated as NH-Sm-MUM-4) with enhanced nonlinear optical (NLO) properties.

A Mononuclear [PtCl(tpy)]PF Complex for a Yellow Emitting Solution-Processable Organic Light Emitting Diode.

We report square planar mononuclear Pt(II)-complexes of terpyridines in the form of [PtCl(/)]PF as phosphorescent emitters (where = 4-(3-pyridine)2,2':6',2''-terpyridine and = 4'-(3-pyridinyl)-4,4''-di(-butyl)-2,2':6'2''-terpyridine). Complex showed emission at 534 nm in the DCM solution with photoluminescence quantum efficiency (Φ) = 14%, while in the mCBP host (5-wt % doped), the emission shifted to 584 nm with Φ = 37.8% and a phosphorescence lifetime (τ) of 37.

A Well-Defined Magnesium Complex of C .

Controlling and understanding charge state and metal coordination in carbon nanomaterials is crucial to harnessing their unique properties. Here we describe the synthesis of the well-defined fulleride complex [{(nacnac)Mg}C], 2, (nacnac)=HC(MeCNMes), Mes=2,4,6-MeCH, from the reaction of the β-diketiminate magnesium(I) complex [{(nacnac)Mg}] with C in aromatic solvents. The molecular structure of complex 2 was determined, providing the first high-quality structural study of a complex with the C ion.

Alkyl backbone variations in common β-diketiminate ligands and applications to -heterocyclic silylene chemistry.

We report the extension of the common β-diketimine proligand class, nacnacH (HC(RCNAr)H), where R is an alkyl group such as Et or iPr, plus Ph, and Ar is a sterically demanding aryl substituent such as Dip = 2,6-diispropylphenyl, Dep = 2,6-diethylphenyl, Mes = 2,4,6-trimethylphenyl or mesityl, Xyl = 2,6-dimethylphenyl, one-pot condensation procedures. When a condensation reaction is carried out using the chemical dehydrating agent PPSE (polyphosphoric acid trimethylsilylester), β-diketiminate phosphorus(V) products such as (nacnac)PO can also be obtained, which can be converted to the respective proligand nacnacH alkaline hydrolysis. The nacnacH proligands can be converted to their alkali metal complexes with common methods and we have found that deprotonation of nacnacH is significantly more sluggish than that of related β-diketimines with smaller backbone alkyl groups.

Anticancer, antimicrobial and photocatalytic activities of a new pyrazole containing thiosemicarbazone ligand and its Co(III) and Ni(II) complexes: Synthesis, spectroscopic characterization and X-ray crystallography.

A new pyrazole based thiosemicarbazone ligand, 5-methyl-3-formylpyrazole-N(4)-isopropylthiosemicarbazone, (HMPNHPr) (compound I), and its cobalt(III) and nickel(II) complexes, [Co(MPNHPr)]Cl (compound II) and [Ni(HMPNHPr)]Br (compound III), respectively, have been synthesized and characterized through various physico-chemical and spectroscopic studies. Both the reported Co(III) and Ni(II) complexes are cationic in nature and behave as 1:1 and 1:2 electrolytes in MeOH, respectively. Electronic spectral features of the complexes have classified them as distorted octahedral ones.

A Boron, Nitrogen, and Oxygen Doped π-Extended Helical Pure Blue Multiresonant Thermally Activated Delayed Fluorescent Emitter for Organic Light Emitting Diodes That Shows Fast k Without the Use of Heavy Atoms.

Narrowband emissive multiresonant thermally activated delayed fluorescence (MR-TADF) emitters are a promising solution to achieve the current industry-targeted color standard, Rec. BT.2020-2, for blue color without using optical filters, aiming for high-efficiency organic light-emitting diodes (OLEDs).

Ligand Hydrogenation during Hydroformylation Catalysis Detected by In Situ High-Pressure Infra-Red Spectroscopic Analysis of a Rhodium/Phospholene-Phosphite Catalyst.

Phospholane-phosphites are known to show highly unusual selectivity towards branched aldehydes in the hydroformylation of terminal alkenes. This paper describes the synthesis of hitherto unknown unsaturated phospholene borane precursors and their conversion to the corresponding phospholene-phosphites. The relative stereochemistry of one of these ligands and its Pd complex was assigned with the aid of X-ray crystal structure determinations.

Thermal Rearrangement of Thiocarbonyl-Stabilised Triphenylphosphonium Ylides Leading to ()-1-Diphenylphosphino-2-(phenylsulfenyl)alkenes and Their Coordination Chemistry.

While thiocarbonyl-stabilised phosphonium ylides generally react upon flash vacuum pyrolysis by the extrusion of PhPS to give alkynes in an analogous way to their carbonyl-stabilised analogues, two examples with a hydrogen atom on the ylidic carbon are found to undergo a quite different process. The net transfer of a phenyl group from P to S gives ()-configured 1-diphenylphosphino-2-(phenylsulfenyl)alkenes in a novel isomerisation process via intermediate λ-1,2-thiaphosphetes. These prove to be versatile hemilabile ligands with a total of seven complexes prepared involving five different transition metals.

Organosolv Pretreatment of Cocoa Pod Husks: Isolation, Analysis, and Use of Lignin from an Abundant Waste Product.

Cocoa pod husks (CPHs) represent an underutilized component of the chocolate manufacturing process. While industry's current focus is understandably on the cocoa beans, the husks make up around 75 wt % of the fruit. Previous studies have been dominated by the carbohydrate polymers present in CPHs, but this work highlights the presence of the biopolymer lignin in this biomass.

Low-Coordinate Magnesium Sulfide and Selenide Complexes.

The reactions of [{(NacNac)Mg}] (nacnac = HC(iPrCNDip)) with PhP═O at 100 °C afforded the phosphinate complex [(NacNac)Mg(OPPh)(OPPh)] . Reactions of with PhP═E (E = S, Se) proceeded rapidly at room temperature to low-coordinate chalcogenide complexes [{(NacNac)Mg}(μ-S)] and [{(NacNac)Mg}(μ-Se)] , respectively. Similarly, reactions of NHC═S ((MeCNR)C═S with R = Me, Et, or Pr) with afforded NHC adducts of magnesium sulfide complexes, [{(NacNac)Mg(NHC)}(μ-S){Mg(NacNac)}] , that could alternatively be obtained by adding the appropriate NHC to sulfide complex .

Phosphine and Selenoether -Substituted Acenaphthenes and Their Transition-Metal Complexes: Structural and NMR Investigations.

A series of -substituted acenaphthene-based phosphine selenoether bidentate ligands Acenap(PrP)(SeAr) (-, Acenap = acenaphthene-5,6-diyl, Ar = Ph, mesityl, 2,4,6-trisopropylphenyl and supermesityl) were prepared. The rigid acenaphthene framework induces a forced overlap of the phosphine and selenoether lone pairs, resulting in a large magnitude of through-space coupling, ranging from 452 to 545 Hz. These rigid ligands - were used to prepare a series of selected late d-block metals, mercury, and borane complexes, which were characterized, including by multinuclear NMR and single-crystal X-ray diffraction.

Methyl 4-amino-3-meth-oxy-isoxazole-5-carboxyl-ate.

The title compound, CHNO, a new derivative of isoxazole, has been synthesized and structurally characterized. The crystal structure shows the mol-ecule to be almost planar (r.m.

Room-Temperature Multiple Phosphorescence from Functionalized Corannulenes: Temperature Sensing and Afterglow Organic Light-Emitting Diode.

Corannulene-derived materials have been extensively explored in energy storage and solar cells, however, are rarely documented as emitters in light-emitting sensors and organic light-emitting diodes (OLEDs), due to low exciton utilization. Here, we report a family of multi-donor and acceptor (multi-D-A) motifs, TCzPhCor, TDMACPhCor, and TPXZPhCor, using corannulene as the acceptor and carbazole (Cz), 9,10-dihydro-9,10-dimethylacridine (DMAC), and phenoxazine (PXZ) as the donor, respectively. By decorating corannulene with different donors, multiple phosphorescence is realized.

A Dual-Purpose Ce(III)-Organic Framework with Amine Groups and Open Metal Sites: Third-Order Nonlinear Optical Activity and Catalytic CO Fixation.

The present work focuses on the synthesis and properties of a novel multifunctional cerium(III) MOF, [Ce(data)(DMF)]·DMF (data: 2,5-diaminoterephthalate), abbreviated as NH-Ce-MUM-2. Its crystal structure reveals an intricate 3D 4,5-connected framework with a topology. This MOF features unique properties, such as open metal sites, presence of free amino groups, and high stability.

Enantioselective isothiourea-catalysed reversible Michael addition of aryl esters to 2-benzylidene malononitriles.

Catalytic enantioselective transformations usually rely upon optimal enantioselectivity being observed in kinetically controlled reaction processes, with energy differences between diastereoisomeric transition state energies translating to stereoisomeric product ratios. Herein, stereoselectivity resulting from an unusual reversible Michael addition of an aryl ester to 2-benzylidene malononitrile electrophiles using an isothiourea as a Lewis base catalyst is demonstrated. Notably, the basicity of the aryloxide component and reactivity of the isothiourea Lewis base both affect the observed product selectivity, with control studies and crossover experiments indicating the feasibility of a constructive reversible Michael addition from the desired product.

A new class of third-order nonlinear optical materials: laser pulse-duration dependant saturable absorption and nonlinear refraction in platinum(II) diimine-dithiolate complexes.

The third-order nonlinear optical (NLO) properties of a series of platinum diimine-dithiolate complexes [Pt(N^N)(S^S)] were investigated by means of -scan measurements, revealing second hyperpolarizability values up to 10 esu, saturable absorption properties, and nonlinear refractive behaviour, which were rationalized also by means of DFT calculations.

Manipulation of the Structure and Optoelectronic Properties through Bromine Inclusion in a Layered Lead Bromide Perovskite.

One of the great advantages of organic-inorganic metal halides is that their structures and properties are highly tuneable and this is important when optimizing materials for photovoltaics or other optoelectronic devices. One of the most common and effective ways of tuning the electronic structure is through anion substitution. Here, we report the inclusion of bromine into the layered perovskite [HN(CH)NH]PbBr to form [HN(CH)NH]PbBr·Br, which contains molecular bromine (Br) intercalated between the layers of corner-sharing PbBr octahedra.

Azaborine as a Versatile Weak Donor for Thermally Activated Delayed Fluorescence.

Extensive research has been devoted to the development of thermally activated delayed fluorescence emitters, especially those showing pure-blue emission for use in lighting and full-color display applications. Toward that goal, herein we report a novel weak donor, 1,4-azaborine (AZB), with complementary electronic and structural properties compared to the widely used dimethylacridan (DMAC) or carbazole (Cz) donors. Coupled with a triazine acceptor, is the direct structural analogue of the high-performance and well-studied green TADF emitter and has Δ = 0.