Search Results (32)

Methylbutynol (MB) is a typical propargylic alcohol with both alkynyl and hydroxyl groups, featuring excellent modifiability and broad applications. Currently, it is produced through the reaction of alkaline metallic acetylides and acetone, requiring expensive raw material and harsh reaction conditions. Herein, a novel method was proposed by replacing the metallic acetylide with calcium carbide (CaC₂) as a low-cost industrial acetylide reagent. The effects of solvent, activator, and proton donor on the ball mill reaction, and the defoaming performance of the resultant MB and its oxidative coupling product (2,7-dimethyl-3,5-octadiyn-2,7-diol), were studied. Nucleophilic reactivity of CaC₂ with acetone can be regulated by the activating effect of the ball mill, an appropriate activator, and a proton donor. High yield of MB (~94%) was obtained under synergistic action of TBAF·3H₂O and acetylene, which represents a facile synthesis process of MB under mild conditions. MB exhibits good defoaming performance, and 2,7-dimethyl-3,5-octadiyn-2,7-diol is more promising, being an excellent non-ionic defoamer. The result is of great significance for exploring new chemical reactions of CaC₂ and its high-value utilizations. Full article

Reppe’s ethynylation of formaldehyde uses coal-based acetylene to produce commercially valuable 1,4-butynediol with a silica-supported copper oxide-bismuth oxide catalyst. Cuprous acetylide (Cu₂C₂) is generally accepted to be the catalytically active phase, which is formed in situ from the CuO-Bi₂O₃/SiO₂ pre-catalyst under ethynylation conditions. The catalytic performance and stability of this sensitive Cu₂C₂ phase are evaluated by long-term experiments (up to 240 h) and by catalyst recycling (10 cycles of 22 h). Powder X-ray diffraction and Raman spectroscopy are found to be the best and the only applicable analytical tools for qualitative evaluation of Cu₂C₂’s crystallinity, purity, and morphology during in situ formation and for phase transformations during the ethynylation. They were continuously correlated with the catalytic performance (1,4-butynediol yield determined by gas chromatography). No catalyst deactivation was observed, indicating outstanding catalyst stability. Observed structural changes within the active Cu₂C₂ phase have obviously limited influence on the catalytic cycle and performance. Full article

Liquid crystals exhibit unique properties that can be tailored in response to external stimuli. Significant research is directed toward the development of luminescent materials exhibiting liquid crystallinity for various applications. The present work reports Au(I) complexes featuring N-heterocyclic carbene and phenyl acetylide ligands. Metal complexes enable the utilization of the triplet excitons through their inherent spin–orbit coupling, promoting intersystem crossing from singlet (S_n) to triplet (T_n) states to observe room-temperature phosphorescence (RTP). The strong bonds between carbene and Au enhance the thermal stability, and the substituted benzimidazole ring alters the thermodynamic and photophysical properties of the complexes. Incorporating the acetylide ligands with long alkoxy chains led to the formation of liquid crystalline (LC) phases, which exhibited stability over a wide temperature range. Additionally, the luminescence behavior was affected by the ethynyl ligands, and high quantum yields of RTP were observed. This study establishes the development of LC Au(I) complexes with a thermodynamically stable LC mesophase over a wide temperature range for applications in the field of light-emitting functional materials. Full article

The light-sensitive explosive (silver acetylide–silver nitrate, SASN) sprayed on structural surfaces can be synchronously initiated by intense pulsed flash, thereby simulating cold X-ray blow-off events characterized by thermal–mechanical coupling effects. By adjusting the areal density of SASN coatings, proportional blow-off impulse levels can be achieved. To address the challenge of in situ and non-destructive areal density measurement for SASN coatings, this study developed an X-ray fluorescence (XRF) detection system integrated with a six-axis spray robot. Excitation parameters (50 kV, 20 μA) and geometric configuration (6 cm focal distance) were optimized to establish a quadratic calibration model between Ag K_α counts and areal density (0–80 mg/cm²) with high correlation (R² = 0.9987). Validation experiments were conducted on a uniformly coated SASN plate (20 × 20 cm) to evaluate the consistency between XRF and sampling methods. The XRF-measured areal density averaged 12.722 mg/cm² with a coefficient of variation (CV) of 3.19%. The reference value obtained by the sampling method was 12.718 mg/cm² (CV = 1.57%). The relative deviation between the two methods was only 0.03%, confirming the feasibility of XRF for the quantification of SASN coatings. The XRF system completed measurements in 1 h, achieving a 77.8% time reduction compared to conventional sampling (4.5 h), significantly enhancing efficiency. This work provides a reliable solution for in situ and non-destructive quality control of energetic material coatings. Full article

Metal-containing compounds form a large and rapidly expanding group of high-energy materials. Many compounds in this class attract the attention of non-professionals, who may attempt the illegal production of explosives. Several of these substances have been commercially available and pose significant danger if used by terrorists or for criminal purposes. Others are experimental compounds, kinds of curiosities, often created by pyrotechnics enthusiasts, which can present serious risks to both the creators and their immediate surroundings. The internet hosts a vast amount of information, including recipes and discussions on forums, private websites, social media, and more. This paper aims to review the variety of metal-containing explosives and discuss their appeal and potential accessibility to unauthorized individuals. Full article

In this study, novel phosphorescent dipyrido[3,2-a;2′3′-c]phenazine (dppz)–platinum(II)–phenylacetylide complexes were developed to fabricate non-doped organic light-emitting diodes (OLED) by solution-processing. To facilitate the charge carrier injection into the emitting layer (EML), 3,6-di-tert-butylcarbazole-functinalized phenylacetylides were employed. As for the dppz ligand, 9,9-dihexylfluoren-2-yl and 4-hexylthiophen-2-yl side-arms were introduced to the 2,7-positions, which led to reddish orange and red photoluminescence (PL), respectively, in solution and film states (PL wavelength: ca. 600 and ca. 625 nm, respectively). The carbazole-appended phenylacetylide ligands hardly affected the emission color, although unsubstituted phenylacetylides gave rise to aggregate- or excimer-based near-infrared PL with a low quantum yield. Two types of non-doped OLEDs were fabricated: single-layer and multilayer devices. In both devices, the organic layers were fabricated by spin-coating, and the EML consisted of a neat film of the corresponding platinum(II) complex. Therein, electroluminescence spectra corresponding to those of PL were observed. The single-layer devices exhibited low device efficiencies due to a deteriorated charge carrier balance. The multilayer devices possessed hole- and electron-transporting layers on the anode and cathode sides of the EML, respectively. Owing to an improved charge carrier balance, the multilayer devices exhibited higher device performance, affording considerably improved values of luminance and external quantum efficiency. Full article

Diblock conjugated oligomers are π-conjugated molecules that contain two segments having distinct frontier orbital energies and HOMO-LUMO gap offsets. These oligomers are of fundamental interest to understand how the distinct π-conjugated segments interact and modify their excited state properties. The current paper reports a study of two series of diblock oligomers that contain oligothiophene (T_n) and 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT) segments that are coupled by either ethynyl (-C≡C-) or trans-(-C≡C-)₂Pt(II)(PBu₃)₂ acetylide linkers. In these structures, the T_n segment is electron rich (donor), and the TBT is electron poor (acceptor). The diblock oligomers are characterized by steady-state and time-resolved spectroscopy, including UV-visible absorption, fluorescence, fluorescence lifetimes, and ultrafast transient absorption spectroscopy. Studies are compared in several solvents of different polarity and with different excitation wavelengths. The results reveal that the (-C≡C-) linked oligomers feature a delocalized excited state that takes on a charge transfer (CT) character in more polar media. In the (-C≡C-)₂Pt(II)(PBu₃)₂-linked oligomers, there is weak coupling between the T_n and TBT segments. Consequently, short wavelength excitation selectively excites the T_n segment, which then undergoes ultrafast energy transfer (~1 ps) to afford a TBT-localized excited state. Full article

A concise synthesis of the sex pheromones of elm spanworm as well as painted apple moth has been achieved. The key steps were the alkylation of acetylide ion, Sharpless asymmetric epoxidation and Brown’s P2-Ni reduction. This approach provided the sex pheromone of the elm spanworm (1) in 31% total yield and those of the painted apple moth (2, 3) in 26% and 32% total yields. The ee values of three final products were up to 99%. The synthesized pheromones hold promising potential for use in the management and control of these pests. Full article

Four couples of 5,6-membered bis(metallacyclic) Pt(II) complexes with acetylide and isocyanide auxiliary ligands have been prepared and characterized. The structures of (−)-2 and (−)-3 are confirmed by single-crystal X-ray diffraction, showing a distorted square-planar coordination environment around the Pt(II) nucleus. Both solutions and solid samples of all complexes are emissive at RT. Acetylide-coordinated Pt(II) complexes have a lower energy emission than those isocyanide-coordinated ones. The emission spectra of N^N′*C-coordinated Pt(II) derivatives show a lower energy emission maximum relative to N^C*N′-coordinated complexes with the same auxiliary ligand. Moreover, the difference between cyclometalated N^N′*C and N^C*N′ ligands exerts a more remarkable effect on the emission than the auxiliary ligands acetylide and isocyanide. Cytotoxicity and cell imaging of luminescent 5,6-membered bis(metallacyclic) Pt(II) complexes have been evaluated. Full article

In this work the rovibrational spectrum of the acetylide anion HCC${}^{-}$ is investigated using high-level electronic structure methods and variational rovibrational calculations. Using a composite approach the potential energy surface and dipole surface is constructed from explicitly correlated coupled-cluster accounting for corrections due to core-valence correlation, scalar relativistic effects and higher-order excitation effects. Previous approaches for approximating the latter are critically evaluated. Employing the composite potential, accurate spectroscopic parameters determined from variational calculations are presented. In comparison to the few available reference data the present results show excellent agreement with ground state rotational constants within 0.005% of the experimental value. Intensities determined from the variational calculations suggest the bending fundamental transition ${\nu }_2$ around 510 cm${}^{-1}$ to be the best target for detection. The rather weak CD stretching fundamental ${\nu }_1$ in deuterated isotopologues show a second-order resonance with the $(0,2^0,1)$ state and the consequences are discussed in some detail. The spectroscopic parameters and band intensities provided for a number of vibrational bands in isotopologues of the acetylide anion should facilitate future spectroscopic investigations. Full article

Dehydrogenative borylation of terminal alkynes has recently emerged as an atom-economical one-step alternative to traditional alkyne borylation methodologies. Using lithium aminoborohydrides, formed in situ from the corresponding amine-boranes and n-butyllithium, a variety of aromatic and aliphatic terminal alkyne substrates were successfully borylated in high yield. The potential to form mono-, di-, and tri-B-alkynylated products has been shown, though the mono-product is primarily generated using the presented condition. The reaction has been demonstrated at large (up to 50 mmol) scale, and the products are stable to column chromatography as well as acidic and basic aqueous conditions. Alternately, the dehydroborylation can be achieved by treating alkynyllithiums with amine-boranes. In that respect, aldehydes can act as starting materials by conversion to the 1,1-dibromoolefin and in situ rearrangement to the lithium acetylide. Full article

Nowadays, the click reaction of azides with alkynes has evolved rapidly and become one of the most efficient methods to synthesize 1,2,3-triazoles, which are an important class of N-containing heterocycles. While the 1,4-selective click reaction of azides with alkynes is well established to synthesize 1,4-substituted 1,2,3-triazoles, the corresponding 1,5-selective click reaction for the generation of 1,5-substituted-1,2,3-triazoles is much less explored, and there is no systematic review for the 1,5-selective click reaction. This timely review summarizes the discovery and development of 1,5-selective click reactions of azides with alkynes for the synthesis of 1,5-substituted 1,2,3-triazoles. The 1,5-selective click reactions will be divided into three types according to the critical reactive intermediates: metallacyclic intermediates, acetylide intermediate, and formal 1,5-selective azide-alkyne cycloaddition. The related mechanistic studies will also be involved in this review. Full article

In this work, we report the synthesis and characterization of a mono-nuclear “two wall” aryl-extended calix[4]pyrrole receptor (2Au) decorated with an acetylide-gold(I)-PTA complex at its upper rim. We describe the ¹H NMR titration experiments of 2Au and its “two wall” aryl-extended calix[4]pyrrole synthetic precursors: the non-symmetric mono-iodo-mono-ethynyl 2 and the symmetric bis-iodo 3 with TBACl in dichloromethane and acetone solution. In acetone solution, we use isothermal titration calorimetry (ITC) experiments to thermodynamically characterize the formed 1:1 chloride complexes and perform pair-wise competitive binding experiments. In both solvents, we measured a decrease in the binding constant of the mono-nuclear 2Au complex for chloride compared to the parent mono-iodo-mono-ethynyl 2. In turn, receptor 2 also shows a reduction in binding affinity for chloride compared to its precursor bis-iodo calix[4]pyrrole 3. The free energy differences (∆G) of the 1:1 chloride complexes cannot be exclusively attributed to their dissimilar electrostatic surface potential values either at the center of the meso-phenyl wall or its para-substituent. We conclude that solvation/desolvation processes play an important role in the stabilization of the chloride complexes. In acetone solution and in the presence of TBACl, 6Au, a reference compound for the acetylide Au(I)•PTA unit, produces a bis(alkynyl)gold(I) anionic complex [7Au]⁻. Thus, the observation of two separate sets of signals for the bound aromatic calix[4]pyrrole protons, when more than 1 equiv. of the salt is added, is assigned to the formation of the chloride complexes of 2Au and of the “in situ” formed calix[4]pyrrole anionic dimer [8Au]⁻. Finally, preliminary data obtained in cell viability assays of 2Au and 6Au with human cancer cells lines assign them with moderate activities showing that the calix[4]pyrrole unit is not relevant. Full article

Focused electron beam induced deposition (FEBID) is a versatile tool to produce nanostructures through electron-induced decomposition of metal-containing precursor molecules. However, the metal content of the resulting materials is often low. Using different Ag(I) complexes, this study shows that the precursor performance depends critically on the molecular structure. This includes Ag(I) 2,2-dimethylbutanoate, which yields high Ag contents in FEBID, as well as similar aliphatic Ag(I) carboxylates, aromatic Ag(I) benzoate, and the acetylide Ag(I) 3,3-dimethylbutynyl. The compounds were sublimated on inert surfaces and their electron-induced decomposition was monitored by electron-stimulated desorption (ESD) experiments in ultrahigh vacuum and by reflection−absorption infrared spectroscopy (RAIRS). The results reveal that Ag(I) carboxylates with aliphatic side chains are particularly favourable for FEBID. Following electron impact ionization, they fragment by loss of volatile CO₂. The remaining alkyl radical converts to a stable and equally volatile alkene. The lower decomposition efficiency of Ag(I) benzoate and Ag(I) 3,3-dimethylbutynyl is explained by calculated average local ionization energies (ALIE) which reveal that ionization from the unsaturated carbon units competes with ionization from the coordinate bond to Ag. This can stabilise the ionized complex with respect to fragmentation. This insight provides guidance with respect to the design of novel FEBID precursors. Full article

Copper dithiocarbamate complexes have been known for ca. 120 years and find relevance in biology and medicine, especially as anticancer agents and applications in materials science as a single-source precursor (SSPs) to nanoscale copper sulfides. Dithiocarbamates support Cu(I), Cu(II) and Cu(III) and show a rich and diverse coordination chemistry. Homoleptic [Cu(S₂CNR₂)₂] are most common, being known for hundreds of substituents. All contain a Cu(II) centre, being either monomeric (distorted square planar) or dimeric (distorted trigonal bipyramidal) in the solid state, the latter being held together by intermolecular C···S interactions. Their d⁹ electronic configuration renders them paramagnetic and thus readily detected by electron paramagnetic resonance (EPR) spectroscopy. Reaction with a range of oxidants affords d⁸ Cu(III) complexes, [Cu(S₂CNR₂)₂][X], in which copper remains in a square-planar geometry, but Cu–S bonds shorten by ca. 0.1 Å. These show a wide range of different structural motifs in the solid-state, varying with changes in anion and dithiocarbamate substituents. Cu(I) complexes, [Cu(S₂CNR₂)₂]⁻, are (briefly) accessible in an electrochemical cell, and the only stable example is recently reported [Cu(S₂CNH₂)₂][NH₄]·H₂O. Others readily lose a dithiocarbamate and the d¹⁰ centres can either be trapped with other coordinating ligands, especially phosphines, or form clusters with tetrahedral [Cu(μ₃-S₂CNR₂)]₄ being most common. Over the past decade, a wide range of Cu(I) dithiocarbamate clusters have been prepared and structurally characterised with nuclearities of 3–28, especially exciting being those with interstitial hydride and/or acetylide co-ligands. A range of mixed-valence Cu(I)–Cu(II) and Cu(II)–Cu(III) complexes are known, many of which show novel physical properties, and one Cu(I)–Cu(II)–Cu(III) species has been reported. Copper dithiocarbamates have been widely used as SSPs to nanoscale copper sulfides, allowing control over the phase, particle size and morphology of nanomaterials, and thus giving access to materials with tuneable physical properties. The identification of copper in a range of neurological diseases and the use of disulfiram as a drug for over 50 years makes understanding of the biological formation and action of [Cu(S₂CNEt₂)₂] especially important. Furthermore, the finding that it and related Cu(II) dithiocarbamates are active anticancer agents has pushed them to the fore in studies of metal-based biomedicines. Full article