Facile oxidative amination with imidazole and L-histidine coordinated cobaloximes.

The simple, robust, and synthetically adaptable cobaloxime core provides an ideal catalytic model for photo- and electrocatalytic H production. Water solubility, oxygen tolerance, and acid stability make these catalysts appealing for sustainable chemistry applications. In this study, we explored cobaloximes with axial imidazole or L-histidine coordination [Co-DMG-X; imidazole, histidine] in photocatalytic hydrogen atom transfer (HAT) reactions for the synthesis of -arylazoles from arenes and azoles.

Lead-Free Tin-Based Halide Perovskites: A Bifunctional Catalyst for Oxygen Evolution and Oxygen Reduction Suitable for Sustainable Energy Applications.

Developing bifunctional electrocatalysts capable of efficiently driving the interconversion between oxygen and water molecules via oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is crucial for establishing renewable-driven energy infrastructure. A series of lead-free halide perovskites CsSnX (X = Cl, Br, I) is designed, along with their mixed halide derivatives CsSnClBr (where x = 2, 3, 4), to probe bifunctional OER/ORR activity. Measurements reveal the influence of halide ions on the morphology and unravel the unique halide-electronegativity-tunable electronic properties.

Electrochemical Screening of Nickel, Copper, and Manganese meso-Aryl Dipyrrinato Complexes Probing Electrocatalytic Hydrogen Evolution.

A series of homoleptic meso-aryl dipyrrinato 1(a-c) and 2(a-c) complexes namely, [(p-R-CH)C(CHN)]M [where, R = OMe, n = 2, M = Ni (1a), Cu (1b) and n = 3, Mn (1c); and R = t-Bu, n = 2, M = Ni (2a), Cu (2b) and n = 3, Mn (2c)] have been synthesized in moderate (ca. 21%-31%) yields. The spectral and structural studies revealed that nickel(II) (1-2)a and copper(II) (1-2)b complexes adopted distorted square planar geometry, whereas Mn(III) (1-2)c exhibited octahedral geometry metal centre.

Pyridine Homopolymers Axial Ligation on Cobaloxime for Efficient Hydrogen Production.

Photocatalytic hydrogen (H) production by mimicking natural light-harvesting complexes offers a sustainable route to solar fuel generation. Here, a pyridine-based homopolymer-chelated cobalt complex is reported as an efficient and stable catalyst for H production via water splitting. This study introduces a series of reversible addition-fragmentation chain transfer (RAFT)synthesized homopolymers with pyridine moieties that axially coordinate to a cobaloxime core.

Morphology prediction for polymer blend thin films using machine learning.

When two immiscible polymers are spin-coated from a common solvent, they undergo phase separation, resulting in a mesoscale morphology that depends on a host of parameters. The phase-separated morphology plays a pivotal role in determining the potential applications of blend thin films. As a guide to experimentalists, a machine learning-based classification framework is proposed that can predict the morphology of PS/PMMA blend thin films.

A switchable red-emitting fluorophore involving a 7.6.6 defect.

An acridine unit entangled into a macrocyclic derivative forms a very efficient fluorophore featuring the confinements of a 7.6.6 defect.

Dynamic Strain-Engineered Au-Ag Alloy Nano-Seed Network for Enhanced Electrochemical Oxygen Reduction and High-Performance Alkaline Membrane H Air Fuel Cells.

The sluggish oxygen reduction reaction (ORR) is the limiting cathodic reaction for the low-temperature H-Air fuel cell. To overcome the limitations of Pt-based nano-scale materials, this work explores the possibility of a simple Au-Ag alloy-based nanosystem for enhanced fuel cell activity by exploiting their substantial electrocatalytic activity, stability, and durability toward ORR in an alkaline medium. This work further demonstrates how the ORR activity of this simple nanosystem can be further tuned by formulating an Au-Ag nanoalloy and manipulating their surface-ligand chemistry to generate a porous aggregated network structure with enriched crystal defects.

Heavier Chalcogenate-Bridged Manganese Carbonyl Complexes: Synthesis, Reactivity, and Electrochemical Investigation.

The chemistry and electrochemical properties of heavier chalcogen-supported (Se or Te) dimanganese complexes have been described. The photolytic reaction of [Mn(CO)] with NaER [E = S, R = Ph; E = Se, R = Ph; E = Te, R = Ph; E = Se, R = ─CH-p-NMe], followed by [(n-Bu)NI] led to the formation of [(n-Bu)N][(CO)Mn(μ-ER)Mn (CO)]¯ [E = S, R = Ph (1); E = Se, R = Ph (2); E = Te, R = Ph (3); E = Se, R = ─CH-p-NMe (4)] complexes. Complexes 1 and 2 were employed for electrocatalytic hydrogen evolution in the presence of HBF.

Unsupervised Machine Learning Prediction of a Novel 1:3 Intermetallic Phase with the Synthesis of TbIr (PuNi-type) as Experimental Validation.

Crystal structure classification of binary intermetallic structures with 1:3 stoichiometry was done with machine learning algorithms. The data set included 97 features and a total of 2366 reported compounds adopting six different structure types. An unsupervised learning method based on principal component analysis (PCA) followed by clustering using the K-means method was applied to cluster compounds belonging to different structure types.

Crystal structure and Hirshfeld surface analysis of 6-[4-(1-cyclo-hexyl-1-tetra-zol-5-yl)but-oxy]-8-nitro-3,4-di-hydro-quinolin-2(1)-one.

The crystal structure of 6-[4-(1-cyclo-hexyl-1-tetra-zol-5-yl)but-oxy]-8-nitro-3,4-di-hydro-quinolin-2(1)-one, CHNO (), was characterized by single-crystal X-ray diffraction. The primary focus was to establish the position of the nitro group, the mol-ecular conformation, and the role of inter-molecular inter-actions towards the crystal packing of . The crystalline structure is mainly consolidated by π-π, C-H⋯O, C-H⋯N, N⋯C(π) and O⋯C(π) inter-actions.

Efficacy of Redox-Active Cu(II) Dipyrrin Complexes toward Electrochemical Reduction of CO.

New D-A-type catalysts based on Cu (II) complexes ( and ) including dipyrrin ligands with phenothiazine/carbazole as the -substituent have been described. The complexes have been thoroughly characterized by various methods (H, C, ESI-MS, EPR, and UV-vis studies), and structures of both and unequivocally determined by X-ray single crystal analyses. The catalysts and are stable at room temperature and exhibit Faradaic efficiency values of ∼56% () and ∼46% () toward homogeneous reduction of CO to CO.

Pallada-Electrocatalysis Enables Distal Regioselective and Atroposelective Olefination Reactions.

Regioselective and enantioselective C-H functionalization is a valuable method for synthesizing chiral and complex molecules. However, it often requires large amounts of toxic oxidants and high temperature, making it environmentally and economically adverse. Additionally, these traditional approaches generally suffer from regioselectivity and enantioselectivity issues.

Fe(II)-Photoantibiotics for Potential Antibacterial, Antibiofilm, and Infective Wound Healing Applications in Rat Model.

Herein, five Fe(II) complexes, viz., [Fe(,,)](ClO), where ,, = 4'-phenyl-2,2':6',2″-terpyridine (Ph-tpy, ), 4'-(4 aminophenyl) 2,2':6',2″ terpyridine (NH-Phtpy, ), 4-([2,2':6',2''-terpyridin]-4'-yl)-,-dimethylaniline (NMe-Phtpy, ), 4'-(-nitrophenyl)-2.2':6',2″-terpyridine (NO-Phtpy, ), and 4'-(4-trifluoromethylphenyl)-2,2':6',2''-terpyridine (CF-Phtpy, ) were developed and screened for their visible-light-triggered antibacterial activity.

A Molecular Catalyst-Driven Sustainable Zinc-Air Battery Assembly.

Bidirectional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts are key for molecular oxygen-centric renewable energy transduction via metal-air batteries. Here, a molecular cobalt complex is covalently tethered on a strategically functionalized silica surface that displayed both ORR and OER in alkaline media. The detailed X-ray absorbance spectroscopy (XAS) studies indicate that this catalyst retains its intrinsic molecular features while playing a central role during bidirectional electrocatalysis and demonstrating a relatively lower energy gap between O/HO interconversions.

Sonodynamic Cancer Therapy by Mn(I)-tricarbonyl Complexes via Ultrasound-triggered CO Release and ROS Generation.

A novel ferrocene conjugated Mn(I)-tricarbonyl complex viz [Mn(Fc-tpy)(CO)Br] (Mn2) where, Fc-tpy=4'-ferrocenyl-2,2':6',2''-terpyridine was synthesized and fully characterized along with its non-ferrocene analog [Mn(Ph-tpy)(CO)Br] Ph-tpy=4'-phenyl-2,2':6',2''-terpyridine (Mn1) for ultrasound (US) activated anticancer applications. The X-ray structure of Mn2 confirmed its distorted octahedral geometry. Mn1 and Mn2, for the first time, showed US-triggered release of CO and ROS generation (O and OH) in an aqueous solution from any Mn(I)-tricarbonyl complexes, indicating its potential for synergetic CO gas therapy and sonodynamic therapy.

Microwave-Assisted Fabrication of Copper Oxide/N-Doped Carbon Nanocatalyst for Efficient Electrochemical CO Conversion to Liquid Fuels.

Electrochemical CO reduction reaction (CORR), which is driven by electricity generated from renewable energy sources, is a promising technology for sustainably producing carbon-based chemicals or fuels. Several CORR catalysts have been explored to date, among which copper-based electrocatalysts are the most widely known for electrochemical CORR and are extensively studied for their ability to generate an array of products. Their low selectivity, however, hinders their possibility of being used for practical purposes.

Trace Ru Incorporation Boosted CoP Nanorods for Superior Water Electrolysis and Substrate-Paired Electrolysis Toward Value-Added Chemicals in Alkaline Medium.

Electro-valorization of biomass-derived chemicals has ensured sustainable production of value-added products, an effective approach for reducing carbon footprint, through renewable energy. Electrochemical oxidation and reduction reactions in aqueous media using HO as a potential source for active hydrogenated and oxygenated species fulfill the purpose. In this study, Ru─CoP nanorods are explored as a bifunctional electrocatalyst toward valorization of Organics at basic media.

Noble Metal Plasmon-Molecular Catalyst Hybrids for Renewable Energy Relevant Small Molecule Activation.

Significant endeavors have been dedicated to the advancement of materials for artificial photosynthesis, aimed at efficiently harvesting light and catalyzing reactions such as hydrogen production and CO conversion. The application of plasmonic nanomaterials emerges as a promising option for this purpose, owing to their excellent light absorption properties and ability to confine solar energy at the nanoscale. In this regard, coupling plasmonic particles with molecular catalysts offers a pathway to create high-performance hybrid catalysts.

Electrocatalytic Conversion of CO to Formic Acid: A Journey from 3d-Transition Metal-Based Molecular Catalyst Design to Electrolyzer Assembly.

ConspectusElectrochemical CO reduction to obtain formate or formic acid is receiving significant attention as a method to combat the global warming crisis. Significant efforts have been devoted to the advancement of CO reduction techniques over the past few decades. This Account provides a unified discussion on various electrochemical methodologies for CO to formate conversion, with a particular focus on recent advancements in utilizing 3d-transition-metal-based molecular catalysts.

Beyond S and Se: Electrocatalytic Hydrogen Production by Tellurolate-Bridged Co(III)-Mn(I) Heterodinuclear Complexes.

In the pursuit of efficient electrocatalysts for the hydrogen evolution reaction (HER), a series of manganese and cobalt heterodinuclear complexes have been synthesized and characterized that have a stark resemblance with the [NiFe]-hydrogenase active site structure. Irradiation of [Mn(CO)] in the presence of 1.5 eq of [NaEPh] [E = S, Se, Te] followed by reaction with [Cp*CoCl] led to the formation of half-sandwiched trichalcogenate-bridged heterodinuclear complexes [{Mn(CO)}(μ-EPh)(CoCp*)] [E = S (); Se () and Te ()].

A ligand-modulated photostable Mn(I)-carbonyl complex for preferential conversion of CO to CO in water.

A strategically designed redox-active ligand ensures proper electronic balance in an Mn(I)-carbonyl template to induce photostability and water solubility. This newly designed Mn-carbonyl complex showcased rapid CO reduction with preferential production of CO (faradaic efficiency ∼88%) as the only C product in pure water, even from a flue gas resource.

Green H Generation from Seawater Deploying a Bifunctional Hetero-Interfaced CoS-CoFe-Layered Double Hydroxide in an Electrolyzer.

This work illustrates the practicality and economic benefits of employing a hetero-interfaced electrocatalyst (CoS@CoFe-LDH), containing cobalt sulphide and iron-cobalt double-layer hydroxide for large-scale hydrogen generation. Here, the rational synthesis and detailed characterization of the CoS@CoFe-LDH material to unravel its unique heterostructure are essayed. The CoS@CoFe-LDH operates as a bifunctional electrocatalyst to trigger both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline seawater (pH 14.

Cancer phototherapy by CO releasing terpyridine-based Re(I) tricarbonyl complexes ROS generation and NADH oxidation.

Here, we have synthesized and characterized three visible light responsive terpyridine based-Re(I)-tricarbonyl complexes; [Re(CO)(ph-tpy)Cl] (Retp1), [Re(CO)(an-tpy)Cl] (Retp2), and [Re(CO)(py-tpy)Cl] (Retp3) where ph-tpy = 4'-phenyl-2,2':6',2″-terpyridine; an-tpy = 4'-anthracenyl-2,2':6',2″-terpyridine, py-tpy = 4'-pyrenyl-2,2':6',2″-terpyridine. The structures of Retp1 and Retp2 were confirmed from the SC-XRD data, indicating distorted octahedral structures. Unlike traditional PDT agents, these complexes generated reactive oxygen species (ROS) type I and type II pathways and oxidized redox crucial NADH (reduced nicotinamide adenine dinucleotide) upon visible light exposure.

Nanoporous air filtering systems made from renewable sources: benefits and challenges.

There is a crucial need for air purification systems due to increasing air contamination, while conventional air-filtering materials face challenges in eliminating gaseous and particulate pollutants. This review examines the development and characteristics of nanoporous polymeric materials developed from renewable resources, which have rapidly advanced in recent years. These materials offer more sustainable alternatives for nanoporous structures made out of conventional polymers and significantly impact the properties of porous polymers.

Expedited Proton Relay in Enzyme-Inspired Cobaloximes Facilitate Organic Transformations.

Developing a water-soluble, oxygen-tolerant, and acid-stable synthetic H production catalyst is vital for renewable energy infrastructure. To access such an effective catalyst, we strategically incorporated enzyme-inspired, multicomponent outer coordination sphere elements around the cobaloxime (Cl-Co-X) core with suitable axial coordination (X). Our cobaloximes with axial imidazole or L-histidine coordination in photocatalytic HAT including the construction of anilines via a non-canonical cross-coupling approach is found superior compared to commonly used cobaloxime catalysts.