Search Results (10)

In this study, we demonstrate the direct preparation of dihalo-γ-lactams featuring two distinct halogens from dichloroamides using a novel atom exchange radical cyclization (AERC) procedure. This method integrates the established atom transfer radical cyclization (ATRC) with halogen exchange in solution. The technique operates under mild conditions and requires small amounts of metallic copper, serving as both a supplemental activator and reducing agent. Full article

Metal halide perovskite semiconductors have emerged as promising materials for various optoelectronic applications due to their unique crystal structure and outstanding properties. Among different forms, perovskite nanowires (NWs) offer distinct advantages, including a high aspect ratio, superior crystallinity, excellent light absorption, and carrier transport properties, as well as unique anisotropic luminescence properties. Understanding the formation mechanism and structure–property relationship of perovskite NWs is crucial for exploring their potential in optoelectronic devices. In this study, we successfully synthesized all-inorganic halide perovskite NWs with high aspect ratios and an orthorhombic crystal phase using the hot-injection method with controlled reaction conditions and surface ligands. These NWs exhibit excellent optical and electrical properties. Moreover, precise control over the halogen composition through a simple anion exchange process enables the tuning of the bandgap, leading to fluorescence emission, covering a wide range of colors across the visible spectrum. Consequently, these perovskite NWs hold great potential for efficient energy conversion and catalytic applications in photoelectrocatalysis. Full article

Semiconductor chips are packaged in a process that involves creating a path to allow for signals to be exchanged with the outside world and ultimately achieving a form to protect against various external environmental conditions such as heat and moisture. The wire bonding type of packaging is a method in which thin metal wires are bonded to pads to create an electrical connection between the chip and the lead frame. An Epoxy Molding Compound (EMC) can be applied to protect semiconductor chips from external environmental conditions such as heat, shock, and moisture. However, EMC contains halogen elements and sulfides and has hydrophilic properties, which can lead to a corrosive environment. The present study aims to evaluate the influence of chloride, which is a contaminant formed during the PCB manufacturing process. To this end, the galvanic corrosion of bonding wire materials Cu wire, Cu wire alloyed with 1% Pd, and Cu wire coated with Pd was investigated. The first ball bond was bonded to the Al pad and the second stitch bond was bonded to the Au pad of the manufacturing process, after which the galvanic corrosion behavior in the semiconductor packaging module specimen was analyzed. A model of galvanic corrosion behavior was also proposed. Full article

This paper presents methods for the introduction and exchange of substituents in a nucleobase and its nucleosides and nucleotides with emphasis on the C8-position in the purine skeleton. The nucleobase is open for electrophilic and nucleophilic chemistry. The nucleophilic chemistry consists mainly of displacement reactions when the C8-substituent is a good leaving group such as a halogen atom. The heteroatom in amines, sulfides, or oxides is a good nucleophile. Halides are good reaction partners. Metal-promoted cross-coupling reactions are important for carbylations. Direct oxidative metalation reactions using sterically hindered metal amides offer chemo- and regio-selectivity besides functional tolerance and simplicity. The carbon site is highly nucleophilic after metalation and adds electrophiles resulting in chemical bond formation. Conditions for metal-assisted reactions are described for nucleobases and their glycosides. Full article

This work reports the one-pot synthesis of sterically demanding aniline derivatives from aryllithium species utilising trimethylsilyl azide to introduce amine functionalities and conversions to new examples of a common N,N′-chelating ligand system. The reaction of TripLi (Trip = 2,4,6-iPr₃-C₆H₂) with trimethylsilyl azide afforded the silyltriazene TripN₂N(SiMe₃)₂ in situ, which readily reacts with methanol under dinitrogen elimination to the aniline TripNH₂ in good yield. The reaction pathways and by-products of the system have been studied. The extension of this reaction to a much more sterically demanding terphenyl system suggested that TerLi (Ter = 2,6-Trip₂-C₆H₃) slowly reacted with trimethylsilyl azide to form a silyl(terphenyl)triazenide lithium complex in situ, predominantly underwent nitrogen loss to TerN(SiMe₃)Li in parallel, which afforded TerN(SiMe₃)H after workup, and can be deprotected under acidic conditions to form the aniline TerNH₂. TripNH₂ was furthermore converted to the sterically demanding β-diketimines ^RTripnacnacH (=HC{RCN(Trip)}₂H), with R = Me, Et and iPr, in one-pot procedures from the corresponding 1,3-diketones. The bulkiest proligand was employed to synthesise the magnesium hydride complex [{(^iPrTripnacnac)MgH}₂], which shows a distorted dimeric structure caused by the substituents of the sterically demanding ligand moieties. Full article

Two solvated rhenium(IV) complexes with formula [ReCl₄(bpym)]·MeCN (1) and [ReCl₄(bpym)]·CH₃COOH·H₂O (2) (bpym = 2,2′-bipyrimidine) have been prepared and characterized by means of Fourier transform infrared spectroscopy (FT–IR), scanning electron microscopy and energy dispersive X-ray analysis (SEM–EDX), single-crystal X-ray diffraction (XRD) and SQUID magnetometer. 1 and 2 crystallize in the monoclinic system with space groups P2₁/n and P2₁/c, respectively. In both compounds, the Re(IV) ion is six-coordinate and bound to four chloride ions and two nitrogen atoms of a 2,2′-bipyrimidine molecule forming a distorted octahedral geometry around the metal ion. In the crystal packing of 1 and 2, intermolecular halogen⋯halogen and π⋯halogen-type interactions are present. Hydrogen bonds take place only in the crystal structure of 2. Both compounds exhibit a similar crystal framework based on halogen bonds. Variable temperature dc magnetic susceptibility measurements performed on microcrystalline samples of 1 and 2 show a similar magnetic behavior for both compounds, with antiferromagnetic exchange between the Re(IV) ions connected mainly through intermolecular Re-Cl⋯Cl-Re interactions. Full article

Multidentate ligands involving tethered pyridyl groups coordinated to transition metal ions have been frequently used to mimic the 3-histidine (3H), 2-histidine-1-carboxylate (2H1C) brace motifs or other combinations of histidine and carboxylate endogenous ligating residues found in bioinorganic metalloenzymes. It is of interest to immobilize these ligand chelates onto heterogeneous supports. This, however, requires the use of bromine-substituted (chloromethyl)pyridines, whose current synthetic routes involve the use of extremely pyrophoric chemicals, such as n-butyllithium that require cryogenic reaction conditions, and toxic chemicals, such as thionyl chloride, that are challenging to handle and require extensive hazard controls. Herein, we report alternative methodologies towards the syntheses of 2-bromo-6-hydroxymethylpyridine and 2-bromo-6-chloromethylpyridine from inexpensive commercially available 2,6-dibromopyridine using isopropylmagnesium chloride lithium chloride complex (Turbo Grignard) and cyanuric chloride which are easier to handle and require milder reaction conditions than the conventional reagents. Gas chromatography-mass spectrometry (GC-MS) methods were developed and simple ¹H- and ¹³C- nuclear magnetic resonance (NMR) and Fourier-transform infrared (FT-IR) spectroscopies were also used to monitor the conversion of both reaction steps and showed that products could be obtained and isolated through simple workups without the presence of unreacted starting material or undesired overchlorinated 2-chloro-6-chloromethylpyridine side product. Full article

Isotactic (it-) and syndiotactic (st-) poly(methyl methacrylate)s (PMMAs) form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st-) PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl₄ as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN₃. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC) between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH₃CN and was affected by the block lengths and ratios. Full article

A selective and practical bromine–metal exchange on bromoheterocyclics bearing substituents with an acidic proton under non-cryogenic conditions was developed by a simple modification of an existing protocol. Our protocol of using a combination of i-PrMgCl and n-BuLi has not only solved the problem of intermolecular quenching that often occurred when using alkyl lithium alone as the reagent for halogen–lithium exchange, but also offered a highly selective method for performing bromo–metal exchange on dibrominated arene compounds through chelation effect. Full article

The present work reports an efficient synthesis of fluorinated pyridinium salts-based hydrazones under both conventional and eco-friendly ultrasound procedures. The synthetic approach first involves the preparation of halogenated pyridinium salts through the condensation of isonicotinic acid hydrazide (1) with p-fluorobenzaldehyde (2) followed by the nucleophilic alkylation of the resulting N-(4-fluorobenzylidene)isonicotinohydrazide (3) with a different alkyl iodide. The iodide counteranion of 5–10 was subjected to an anion exchange metathesis reaction in the presence of an excess of the appropriate metal salts to afford a new series of fluorinated pyridinium salts tethering a hydrazone linkage 11–40. Ultrasound irradiation led to higher yields in considerably less time than the conventional methods. The newly synthesized ILs were well-characterized with FT-IR, ¹H NMR, ¹³C NMR, ¹¹B, ¹⁹F, ³¹P and mass spectral analyses. The ILs were also screened for their antimicrobial and antitumor activities. Within the series, the salts tethering fluorinated counter anions 11–13, 21–23, 31–33 and 36–38 were found to be more potent against all bacterial and fungal strains at MIC 4–8 µg/mL. The in vitro antiproliferative activity was also investigated against four tumor cell lines (human ductal breast epithelial tumor T47D, human breast adenocarcinoma MCF-7, human epithelial carcinoma HeLa and human epithelial colorectal adenocarcinoma Caco-2) using the MTT assay, which revealed that promising antitumor activity was exhibited by compounds 5, 12 and 14. Full article