A Highly Lewis Acidic Strontium ansa-Arene Complex for Lewis Acid Catalysis and Isobutylene Polymerization

The potential of a dicationic strontium ansa-arene complex for Lewis acid catalysis has been explored. The key to its synthesis was a simple salt metathesis from SrI₂ and 2 Ag[Al(OR^F)₄], giving the base-free strontium-perfluoroalkoxyaluminate Sr[Al(OR^F)₄]₂ (OR^F=OC(CF₃)₃). Addition of an ansa-arene yielded the highly Lewis acidic, dicationic strontium ansa-arene complex. In preliminary experiments, the complex was successfully applied as a catalyst in CO₂-reduction to CH₄ and a surprisingly controlled isobutylene polymerization reaction.     

The Metaphosphite (PO2−) Anion as a Ligand

The utilization of monomeric, lower phosphorous oxides and oxoanions, such as metaphosphite (PO₂⁻), which is the heavier homologue of the common nitrite anion but previously only observed in the gas phase and by matrix isolation, requires new synthetic strategies. Herein, a series of rhenium(I–III) complexes with PO₂⁻ as ligand is reported. Synthetic access was enabled by selective oxygenation of a terminal phosphide complex. Spectroscopic and computational examination revealed slightly stronger σ-donor and comparable π-acceptor properties of PO₂⁻ compared to homologous NO₂⁻, which is one of the archetypal ligands in coordination chemistry.     

Effective one-pot synthesis of tetrahydrobenzo[b]pyran derivatives using nickel Schiff-base complex immobilized on iron oxide nanoparticles

Nickel Schiff-base complex immobilized on silica-coated Fe₃O₄ as a heterogeneous catalyst was designed and characterized by different techniques, such as Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), inductively coupled plasma (ICP) and vibrating sample magnetometry (VSM) thermogravimetric analysis (TGA), and Brunauer–Emmett–Teller (BET). The synthesized nanocatalyst has been explored as a new and efficient recyclable heterogeneous catalyst for the one-pot three-component synthesis of tetrahydrobenzo[b]pyran derivatives. The reaction proceeds smoothly to supply the respective products in excellent yields and low reaction times. The catalyst can be easily recovered by a magnetic field and reused for eight consecutive reaction cycles without significant loss of activity.     

Sustainable synthesis of quinolines (pyridines) catalyzed by a cheap metal Mn(I)-NN complex catalyst

This study represents the first example of a bidentate phosphine-free manganese(I)-NN complex catalyst for the synthesis of quinolines (pyridines) through acceptorless dehydrogenative condensation of various secondary alcohols with amino alcohols. The coupling reactions occurred at 3 mol% catalyst loading and 110°C, and tolerated diverse functional groups. Moderate to excellent yields ranging from 45% to 89% were achieved after 12 hr of reaction. The present protocol provides a concise and environmentally friendly method for the construction of heterocyclic compounds.     

Reversible M−M Bonding by Alkaline Earth Metals (Mg,Ca, Sr,Ba) in Graphite Intercalation Compounds

The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but M^I dimeric complexes with M−M bonding, [M₂(en)₂]²⁺, (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor-type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en)₂]²⁺. Here, the facile interconversion between dimeric-M^I and monomeric-M^II intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X-ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M₂(en)₂]²⁺ or [M(en)₂]²⁺ guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M−M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M⁰→M²⁺ reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage.     

Study on the Interaction and Properties of Cucurbit[8]uril with Oroxin B

The interaction between cucurbit[8]uril(Q[8]) and oroxin B(ORB) was investigated by UV-visible(UV-Vis) spectroscopy, isothermal titration calorimetry(ITC), mass spectrum(MS) and nuclear magnetic resonance(NMR) spectroscopy. The results showed that ORB formed a 2:1 inclusion complex with Q[8] with a binding constant of 8.266×10⁵ L²·mol^-2. ORB had good scavenging ability for 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate)(ABTS) free radicals(IC₅₀=5.74 μmol/L) and the addition of Q[8] did not significantly affect the antioxidant activity of ORB(IC₅₀=5.76 μmol/L). A phase solubility experiment revealed a 1.86-fold increase in the solubility of ORB when c(Q[8])=100 μmol/L. In vitro drug release experiments showed that the release rate for ORB@Q[8] complex was lower than that of ORB in artificial intestinal juice, and higher than that of ORB in artificial gastric juice.     

Two Rare-Earth Molecular Ferroelectrics with High Curie Temperatures,Large Spontaneous Polarization,Switchable Second Harmonic Generation Effects,and Strong Photoluminescence

Smart multifunctional molecular ferroelectrics bearing high Curie temperatures and diverse excellent physical properties, such as second harmonic generation (SHG) responses, luminescence, and semiconductivity, among others, have significant applications but have seldom been documented. Herein, the rare-earth metals Nd and Pr are introduced into a simple molecular system (nBu₄N )₃[M(NO₃)_x(SCN)_y] (nBu₄N₌tetrabutyl ammonium, M=rare-earth metal, nBu=CH₃CH₂CH₂CH₂), and two new multifunctional molecular ferroelectrics are obtained: (nBu₄N )₃[Nd(NO₃)₄(SCN)₂] ( 1 ) and (nBu₄N )₃[Pr(NO₃)₄(SCN)₂] ( 2 ). Their distinct heat and dielectric anomaly dependence on temperature verifies that compounds 1 and 2 experience high-temperature para-ferroelectric phase transitions at 408 and 413 K, respectively. Strikingly, both molecular ferroelectrics possess large spontaneous polarization with P_s values of 9.05 and 8.50 μC cm⁻², respectively, and are further characterized by the appearance of multiple intersecting non-180° domains and polarization switching behavior. In particular, compounds 1 and 2 show good stability with only a small decrease in SHG intensity after switching cycles, suggesting that they have great potential for application in nonlinear optical (NLO) switches. Simultaneously, the rare-earth compounds 1 and 2 present bright yellow–red and bright green fluorescence, respectively, at room temperature.     

Silver chloride supported on Vitamin B1 -Organometallic magnetic catalyst: synthesis,density functional theory study and application in A3-coupling reactions

A highly efficient Fe₃O₄@VitB₁–Ag(I) magnetic catalyst has been obtained using surface modification of Fe₃O₄. To this end, silver chloride was immobilized on Fe₃O₄ nanoparticles via vitamin B₁ biomolecules. The synthesized biocompatible magnetic catalyst was applied in an A³-coupling reaction in the presence of aldehyde, amine and phenyl acetylene under solvent-free conditions and afforded the desired products in excellent yields. Also, interactions between metal and ligand in the Fe₃O₄@VitB₁–Ag(I) were studied using theoretical calculations.     

Synthesis and crystal structure of a new copper (II) complex,designed to produce efficient successor of Cu2O,toward synergy of adsorption and photodegradation of MB

A new copper (II) coordination complex formulated as [Cu (dipic)(phen)(2-MePy)]. 2H₂O ( 1 ) where phen = 1, 10-phenanthroline, dipic²⁻ = pyridine-2,6-dicarboxylato and 2-MePy = 2-methyl pyrrole was synthesized through a simple and environment-friendly reaction under ultrasound irradiation. Also, complex 1 was synthesized by hydrothermal process at 120 °C for 3 days. The corresponding structure of complex 1 was characterized by elemental analysis, atomic absorption spectroscopy (AAS), inductively coupled plasma (ICP), conductivity measurement, Fourier-transform infrared spectroscopy (FT-IR), Raman spectroscopy, ultraviolet–visible spectroscopy (UV–Vis), thermal gravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM) and fluorescence. The crystal structure of the hydrothermally synthesized complex was characterized by single crystal X-ray diffraction (SC-XRD(, which revealed a triclinic structure. In the remainder of this study, the Cu₂O nanoparticles have been prepared via thermal decomposition of hydrothermal and ultrasound complexes and characterized by ICP, FT-IR, powder X-ray diffraction (XRD), SEM and N₂ adsorption/desorption. Adsorption and visible-light-driven photocatalytic capabilities of two synthetic Cu₂O were investigated in the removal of MB from water. The result showed that the synthesized catalysts have good catalytic activity and the photocatalytic degradation is more effective in dye removal of MB compared with the adsorption.     

Promising new catalytic properties of a Co (II)-carboxamide complex and its derived Co3O4 nanoparticles for the Mizoroki-Heck and the Epoxidation reactions

The new Co(II) - carboxamide complex ( 1 ) and Co₃O₄ nanoparticles ( 2 ), by way of thermal decomposition of ( 1 ) have been efficiently synthesised in the environment-friendly. X-ray diffraction reveals a slightly distorted octahedral coordination of cobalt (four nitrogens and two oxygens) in ( 1 ) and regular octahedral or tetrahedral ones (oxygens only) in ( 2 ). The investigation of ( 1 ) and ( 2 ) in the Mizoroki-Heck and epoxidation of alkens reactions showed them both to be powerful, green and inexpensive catalysts.