Sol–gel derived LaFeO3/SiO2 nanocomposite: synthesis,characterization and its application as a new,green and recoverable heterogeneous catalyst for the efficient acetylation of amines,alcohols and phenols

LaFeO₃/SiO₂ nanocomposite was synthesized by the sol–gel process from metal nitrates and tetraethyl orthosilicate (TEOS) as the SiO₂ source. The nanocomposite product was characterized by XRD, FT-IR, SEM, and surface area measurements and was used as a heterogeneous catalyst for the efficient acetylation of amines, alcohols and phenols to the corresponding acetates using acetic anhydride under solvent-free conditions. Among the various substrates, acetylation of amines was preceded rapidly, so that an amine group could be selectively acetylated in the presence of alcoholic or phenolic hydroxyl groups by the appropriate choice of reaction time. The catalyst can also be reused several times without the loss of activity. In addition, the catalytic activity of the LaFeO₃/SiO₂ nanocomposite was higher than that of the pure LaFeO₃ nanoparticles. The method is high yielding, clean, cost effective, compatible with the substrates having other functional groups and very suitable for the practical organic synthesis.     

Platinum electrode modified with polyterthiophene doped with metallic nanoparticles,as sensitive sensor for the electroanalysis of ascorbic acid (AA)

A novel electrochemical sensor for ascorbic acid (AA) detection based on platinum electrode modified with polyterthiophene (P3T) and doped with metallic particles (Cu, Co, Ag, Au, Pd) was constructed. The electrocatalytic performances of the modified electrode with polyterthiophene-metallic particles related to the detection of AA, showed a better catalytic activity compared to the modified electrode with polyterthiophene film. The obtained results demonstrate also that the use of P3T–Ag nanocomposite allows a good sensitivity; which gives a high response in oxidation peak of AA. In order to have a good performance using this sensor, several parameters such as polymerization time of the film and immersion time of the film in AgNO₃ solution were optimized.     

Atomistic Insight Into the Host–Guest Interaction of a Photoresponsive Metal–Organic Framework

Photoresponsive functional materials have gained increasing attention due to their externally tunable properties. Molecular switches embedded in these materials enable the control of phenomena at the atomic level by light. Metal–organic frameworks (MOFs) provide a versatile platform to immobilize these photoresponsive units within defined molecular environments to optimize the intended functionality. For the application of these photoresponsive MOFs (pho-MOFs), it is crucial to understand the influence of the switching state on the host–guest interaction. Therefore, we present a detailed insight into the impact of molecular switching on the intermolecular interactions. By performing atomistic simulations, we revealed that due to different interactions of the guest molecules with the two isomeric states of an azobenzene-functionalized MOF, both the adsorption sites and the orientation of the molecules within the pores are modulated. By shedding light on the host–guest interaction, our study highlights the unique potential of pho-MOFs to tailor molecular interaction by light.     

Complexes of gold(I), silver(I), and copper(I) with pentaaryl[60]fullerides

Gold(I), silver(I), and copper(I) phosphine complexes of 6,9,12,15,18-pentaaryl[60]fullerides 1a and 1b, namely, [(4-MeC(6)H(4))(5)C(60)]Au(PPh(3)) (2a), [(4-t-BuC(6)H(4))(5)C(60)]Au(PPh(3)) (2b), [(4-MeC(6)H(4))(5)C(60)]Ag(PCy(3)) (3a), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PPh(3)) (3b), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PCy(3)) (3c), [(4-MeC(6)H(4))(5)C(60)]Cu(PPh(3)) (4a), and [(4-t-BuC(6)H(4))(5)C(60)]Cu(PPh(3)) (4b), have been synthesized and characterized spectroscopically. All complexes except for 3c were also characterized by single-crystal X-ray diffraction. Several coordination modes between the cyclopentadienyl ring embedded in the fullerene and the metal centers are observed, ranging from η(1) with a slight distortion toward η(3) in the case of gold(I), to η(2)/η(3) for silver(I), and η(5) for copper(I). Silver complexes 3a and 3b are rare examples of crystallographically characterized Ag(I) cyclopentadienyls whose preparation was possible thanks to the steric shielding provided by fullerides 1a and 1b, which stabilizes these complexes. Silver complexes 3a and 3b both display unexpected coordination of the cyclopentadienyl portion of the fulleride anion with Ag(I). DFT calculations on the model systems (H(5)C(60))M(PH(3)) and CpMPH(3) (M = Au, Ag, or Cu) were carried out to probe the geometries and electronic structures of these metal complexes.     

Synthesis and Characterization of Antimony(III) Complexes of Thioamides,and Crystal Structure of {[Sb(Imt)2Cl2]2((2‐Imt)}Cl2(Imt=Imidazolidine‐2‐thione)

Antimony(III) complexes of thioamides [thioamides=thiourea (Tu), N,N′‐dimethylthiourea (Dmtu), tetramethylthiourea (Tmtu), imidazolidine‐2‐thione (Imt) and diazinane‐2‐thione (Diaz)] with the general formulae, Sb(thione)_nCl₃ (n=1, 2, 2.5, 3) were prepared and characterized by elemental analysis, IR and NMR (¹H, ¹³C) spectroscopic methods. The spectral data of the complexes are consistent with the coordination of the thiones to antimony(III). The crystal structure of one of them, {[Sb(Imt)₂Cl₂]₂(μ₂‐Imt)}Cl₂ ( 1 ), was determined by X‐ray crystallography, which shows that the complex is dinuclear consisting of two [Sb(Imt)₂Cl₂] units bridged by an Imt molecule. In 1 , the antimony atom is bonded to two chlorine atoms, two sulfur atoms of coordinated Imt molecules and one sulfur atom of a bridging Imt molecule. The antimony environment can be considered to be distorted octahedral with one Cl^? ion weakly bound to antimony.     

A New and Simple Electrocatalyst for Formaldehyde Oxidation; Nickel/poly(o‐Anisidine)/Film Modified Ionic Liquid Carbon Paste Electrode

In present work, the ionic liquid, 1‐butyl‐3‐methylimidazolium bis (trifluoromethylsulfonyl) imide was incorporated in the carbon paste electrode as the binder (IL‐CPE). O‐anisidine (OA) monomer is electropolymerized in the presence of an aqueous acidic solution onto IL‐CPE (POA/IL‐CPE). The as‐prepared substrate is used as a porous matrix for dispersion of Ni(II) ions by immersing the modified electrode in a nickel(II) nitrite solution. The modified electrodes are characterized by scanning electron microscopy (SEM) and electrochemical methods. The POA/IL‐CPE was applied successfully to highly efficient (current density of 18.2 mA cm^?2) electrocatalytic oxidation of formaldehyde in alkaline medium. Finally, the rate constant for chemical reaction between formaldehyde and redox sites of the electrode was calculated.     

Efficient One‐Pot Four‐Component Synthesis and X‐ray Crystallographic Structure of 2‐Pyridone Derivatives

A series of 3‐cyano‐2‐pyridone derivatives were synthesized by one‐pot four‐component condensation reaction involving a benzaldehyde derivative, alkyl cyanoacetate, acyclic or cyclic ketones, and ammonium acetate in reflux condition. The X‐ray structure of the products 5a and 5d confirm symmetric dimers via hydrogen bonding interactions between individual pyridine molecules showing, in addition, also π–π stacking interactions.     

Solvent-Free Acetylation of Thiols Under Catalysis of MgBr2·OEt2

Solvent-free protection of aromatic and aliphatic thiols with acetic anhydride was performed at room temperature under trace quantities of magnesium bromide ethyl etherate, affording rapid formation of various thiol esters in excellent yields.     

Ab Initio Study of Structures,Metallotropic 1,2-Shifts and Prototropic 1,2-Shifts of Cyclopentadienyl(trimethyl)silane, -germane and -stannane

Molecular structures, metallotropic and prototropic shifts of cyclopentadienyl(trimethyl)silane ( 1 ), cyclopentadienyl(trimethyl)germane ( 2 ), and cyclopentadienyl(trimethyl)stannane ( 3 ) were investigated using ab initio molecular orbital and the Becke, Lee, Yang, and Parr density functional (B3LYP) methods. The results show that the most stable structure of compounds 1-3 has the (CH 3 ) 3 M fragment in the allylic position. The energy barrier of metallotropic shifts in compound 1 is higher than in 2 , and in compound 2 higher than in 3 , in good agreement with experimental data. The cyclopentadienyl rings in compounds 1-3 are found to be planar but this result contradicts the reported experimental data.     

An Ab Initio Study and NBO Analysis of the Stability and Conformational Properties of Hexakis(trimethylelementhyl)benzene (Element = C,Si, Ge,and Sn)

Ab initio molecular orbital and density functional theory were used to investigate energetic and structural properties of the various conformations of hexa-tertbutylbenzene (1), hexakis(trimethylsilyl)benzene (2), hexakis (trimethylgermyl)benzene (3), and hexakis(trimethylstannyl)benzene (4). HF/3-21G//HF/3-21G and B3LYP/3-21G//HF/3-21G results revealed that the Twist-Boat (TB) conformer of compound 1 is more stable than the 1-Chair (C), 1-Boat (B), and 1-Planar (P) conformers. B3LYP/3-21G//HF/3-21G results show that the 1- TB conformer is more stable than 1- C, 1- B, and 1- P conformers of about 1.13, 4.34, and 99.94 kcal mol^?1 , respectively. Contrary to the stability order of compound 1 conformers, the C conformer of compounds 2–4 is more stable than TB, B, and P conformations, as calculated by B3LYP/3-21G//HF/3-21G and HF/3-21G//HF/3-21G levels of theory. The energy gap between the C and P conformers in compounds 1–4 is decreased in the following order: ΔE(4: C, P) < ΔE (3: C, P) < ΔE(2: C, P) < ΔE (1: C, P). This fact can be explained in terms of the increase of C _aromatic -M (M═C, Si, Ge, and Sn) bond lengths and the decrease of steric (van der Waals) repulsions in the previously discussed compounds. For compounds 1–3, the calculations were also performed at the B3LYP/ 6-31G*//HF/3-21G level of theory. However, the comparison showed that the results at B3LYP/3-21G//HF/3-21G methods correlated well with those obtained at the B3LYP/6-31G*// HF/6-31G method. Further, NBO analysis revealed that in compounds 1–4, the resonance energy associated with the σ_M-C1 to σ*_C2-C3 delocalization is 5.20, 9.68, 11.15, and 12.27 kcal mol^?1, respectively. These resonance energy values could explain the easiness of the ring flipping processes of C, B, and TB conformers of compounds 4 to 1. Also, the NBO results showed that by an increase of the σ_M-C1 → σ *_C2-C3 resonance energies in compounds 1–4, the σ_M-C1 bonding orbital occupancies decrease. This fact could fairly explain the increase of the C_aryl-M bond length from compound 1 to 4. The NBO results are also in good agreement with the calculated energy barriers for the ring flipping of the chair conformations in compounds 1–4, as calculated by B3LYP and HF methods.