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101.
《Angewandte Chemie (International ed. in English)》2017,56(4):1152-1157
Supramolecular capsules were assembled by neutral halogen bonding (XB) and studied in the solid state, in solution, and in the gas phase. The geometry of the highly organized capsules is shown by an X‐ray crystal structure which features the assembly of two XB hemispheres, geometrically rigidified by H‐bonding to eight MeOH molecules and encapsulation of two benzene guests. To enhance capsular association strength, tuning the XB donor is more efficient than tuning the XB acceptor, due to desolvation penalties in protic solvents, as shown for a tetraquinuclidine XB acceptor hemisphere. With a tetra(iodoethynyl) XB donor and a tetralutidine XB acceptor, the association in deuterated benzene/acetone/methanol 70:30:1 at 283 K reaches K a=(2.11±0.39)×105 m −1 (ΔG =−6.9±0.1 kcal mol−1). The stability of the XB capsules in the gas phase was confirmed by electrospray ionization mass spectrometry (ESI‐MS). A new guest binding site was uncovered within the elongated iodoethynyl capsule. 相似文献
102.
《Angewandte Chemie (International ed. in English)》2017,56(39):11990-11994
As an emerging member of endohedral fullerenes, metal cyanide clusterfullerenes (CYCF) are unique in terms of the encapsulation of a monometallic cluster. To date the reported carbon cages of CYCFs are limited to C82 and C76, and little is known about the chemical reactivity of CYCFs. Herein, two isomers of the first C84‐based CYCFs, YCN@C84, were isolated as trifluoromethyl derivatives, including YCN@C84(23)(CF3)18 and three isomers of YCN@C84(13)(CF3)16, which are based on a unique chiral C 2‐C84(13) cage. As a common feature of the CF3 addition patterns, the YCN@C84(CF3)16/18 compounds are stabilized by the formation of isolated C=C bonds and benzenoid rings on the carbon cages. The interplay between the endohedral YCN cluster and the exhohedral CF3 addends was unveiled according to single‐crystal X‐ray diffraction studies, thus offering new insight into the chemical reactivity of CYCFs. 相似文献
103.
Quentin Vanbellingen Paul Servin Anaïs Coinaud Sonia Mallet-Ladeira Rgis Laurent Anne-Marie Caminade 《Molecules (Basel, Switzerland)》2021,26(8)
Pyridine, pyridine imine, and bipyridine imine ligands functionalized by a phenol have been synthesized and characterized, in many cases by X-ray diffraction. Several of these N-, N,N-, and N,N,N,-ligands have been grafted onto the surface of phosphorhydrazone dendrimers, from generation 1 to generation 3. The complexation ability of these monomers and dendrimers towards palladium(II) has been assayed. The corresponding complexes have been either isolated or prepared in situ. In both cases, the monomeric and dendritic complexes have been tested as catalysts in Heck couplings and in Sonogashira couplings. In some cases, a positive dendritic effect has been observed, that is, an increase of the catalytic efficiency proportional to the dendrimer generation. 相似文献
104.
Denisa Dumitrescu Sergiu Shova Constantin Draghici Marcel Mirel Popa Florea Dumitrascu 《Molecules (Basel, Switzerland)》2021,26(12)
3-Arylsydnones bearing fluorine and bromine atoms on the benzene ring were synthesized from N-nitroso-2-fluorophenylglycines and characterized by NMR spectroscopy. These were employed further in synthesis of the corresponding 1-(2-fluorophenyl)pyrazoles by 1,3-dipolar cycloaddition reaction with dimethyl acetylenedicarboxylate (DMAD) as activated dipolarophile. The sydnones as reaction intermediates were characterized by single crystal X-ray diffraction analysis showing interesting features such as halogen bonding as an important interaction in modeling the crystal structure. 相似文献
105.
E.A. Gusakov O.P. Demidov I.O. Tupaeva E.V. Vetrova M.A. Soldatov A.A. Tereshchenko A.D. Dubonosov Y.A. Sayapin A.V. Metelitsa V.I. Minkin 《Materials Today Chemistry》2021
The first representative of a new class of charge transfer complexes for organic semiconductors was synthesized. The reaction of p-nitroaniline (PNA) with [1,10]-phenanthroline-5,6-dione (PD) results in the formation of a stable molecular charge transfer (CT) complex PNA3-PD2 in a ratio of 3:2. The structure of the molecular CT complex PNA3-PD2 was established by X-ray diffraction studies. Using the density functional theory method, it is shown that several types of intermolecular interactions are realized in the complex: between the PNA amino group and the nitro group of another PNA molecule, carbonyl groups, and PD nitrogen atoms. Complex PNA3-PD2 is stable only in solid form. The diffuse reflectance UV–vis spectrum of PNA3-PD2 crystal powder is characterized by the intense weakly structured long-wavelength absorption band up to 650 nm. Quantum chemical calculations of the electronic structure have shown that the complex PNA3-PD2 is a straight-band semiconductor with a band gap of 2.11 eV. 相似文献
106.
Depending on the solvothermal reaction conditions, we obtained three different metal-organic frameworks with yttrium(III) as metal component and 2,5-dihdyroxyterepthalic acid (H4dhtp) as bifunctional organic linker: Y2(H2dhtp)3(dmf)4 · (dmf)2 (CPO-29) contains dinuclear, paddle-wheel like inorganic secondary building units (SBUs) connected by the organic linker to a network with α-Po topology, while Y2(H2dhtp)(dhtp)(dmf)2 (CPO-30) and Y2(H2dhtp)(dhtp)(dmf)2(H2O)2 · (H2O)4 (CPO-31) contain one-dimensional inorganic SBUs that differ in how the half- and fully deprotonated ligands are connected to and arranged around them. Only the carboxylic acid groups of the organic linker are deprotonated in CPO-29, while CPO-30 and CPO-31 contain both 2,5-dihydroxyterephthalate (H2dhtp2–) linkers and fully deprotonated 2,5-dioxidoterephthalate (dhtp4–) linkers. All three compounds contain large volumes filled with solvent, but we were able to demonstrate permanence of porosity only for CPO-30. Variable temperature powder X-ray diffraction reveals that CPO-29 and CPO-31 undergo discontinuous phase transitions upon heating, and the flexibility of the framework structure indicated by these might be the reason for the inability to access the pore volume. Desolvated CPO-30 and CPO-31 are polymorphs, whose network structures differ in whether the H2dhtp2– and dhtp4– linkers are located in cis or trans arrangement around the inorganic SBU. 相似文献
107.
Single crystals of a new calcium(II) complex of benzilic acid, [Ca(C14H11O3)2(C14H12O3)2] have been successfully grown by gel diffusion technique at room temperature. Single crystal X-ray diffraction study reveals that the compound belongs to orthorhombic system with space group Fddd. The adjacent CaO8 units are linked via O–H–O interaction to form one dimensional polymeric chains. The extensive hydrogen bonding interactions lead to a supramolecular structure. The grown crystals were further characterized by elemental analysis, FT-IR, UV–Visible, thermogravimetric, powder X-ray diffraction and solid state photoluminescence studies. 相似文献
108.
The worldwide demand for energy continues to grow and the production of heavy crude is escalating due to shortage of conventional light crude. The transportation of heavy crude oil from the head-well to the refinery is a challenging task due to its high viscosity and low API gravity. Catalytic aquathermolysis is one of the most significant and cost-effective viscosity reduction techniques employed in the up gradation of the crude oil at elevated temperatures and hence to enhance oil extraction process. In this study, catalytic aquathermolysis of Omani heavy crude oil was performed using magnetite nanoparticles (NPs). The NPs were synthesised by reverse co-precipitation method using iron salts in alkaline medium. The synthesised NPs were characterized using Scanning Electron Microscopy (SEM), X-Ray Powder Diffraction (XRD), Energy Dispersive X- Ray analysis (EDX) and Fourier Transform Infrared Spectroscopy (FTIR). The XRD results exhibited a characteristic peak confirming the high purity of iron oxide nanoparticles. The FTIR spectral analysis designated two well-defined peaks corresponding to wave numbers of 500 ?cm?1 and 630 ?cm?1, endorses the presence of Fe–O. The catalytic aquathermolysis experiments were carried out in a Parr high temperature-high pressure batch reactor at different experimental conditions. The processing parameters in temperature range of 250 ?°C - 300 ?°C, 0.1% to 0.3% catalyst loading, water to oil ratio of 1:7 to 3:7 with 24–72 ?h of reaction time. The initial pressure in the reactor was maintained at 32 ?bars and the optimization was performed using the Taguchi method to maximize the level of heavy oil. An orthogonal array was employed to analyse the effects of mean response and mean signal-to-noise ratio (S/N) to upgrade the heavy oil. The regression analysis was used to establish a relationship between the viscosity and experimental parameters. The experimental outcomes indicates that the maximum reduction in viscosity occurred at a processing temperature of 300 ?°C, 1:7 ?W/O ratio, 0.1 ?wt% of catalyst concentration and 48 ?h of reaction time. Similarly, the optimum conditions for the reduction in API gravity were obtained at 280 ?°C temperature, 3:7 ?W/O ratio, 0.2 ?wt% of catalyst concentration and a reaction time of 24 ?h. 相似文献
109.
The progress in the development of gas sensors has considerably grown using some novel nanomaterials of metal, metal oxide and composite. In the current study, we intended and evaluated the properties of nanomaterials like CeO2, NiO, and CeO2–NiO composite and its application as NO2 gas sensor. Sensing of low concentration of NO2 gas at optimum functional temperature was succeeded using CeO2–NiO nanocomposites (NCs) film. The working temperature ranges in between 100 and 225 ?°C. Highly crystalline nanomaterials (CeO2, NiO and CeO2–NiO) have been prepared by applying microwave-assisted sol-gel route. The as-prepared nanomaterials are characterized for their structure, size, morphology and constitution by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis. XRD studies of nanoparticles reveal the formation of nanoscale CeO2 and NiO with crystallite size 26, 23 ?nm, respectively. Both are having a face centered cubic structure. The nanocomposite (NC) Ce:Ni ?= ?60:40 has crystallite size of 13 ?nm. XRD study of NCs shows assimilation of Ni metal into the ceria and proves physical similarities of two phases. It can be observed from SEM that prepared NC has a porous surface which enables more surface active sites for adsorbing oxygen. The optical properties are measured with the help of UV–Vis. Spectroscopy. Optical band gaps of 3.19, 3.41 and 2.9 ?eV were observed for CeO2, NiO nanoparticles (NPs) and CeO2–NiO NC, respectively. Gas sensing properties state that the NC material shows a higher gas response % of 67.34% for NO2 gas (25 ?ppm) at comparatively low operating temperature (125 ?°C). It gives response time as (~28 ?s) and the recovery (~54 ?s). NiO incorporation in CeO2 results in a decline of operating temperature of NC and improves the sensing features. 相似文献
110.
An innovative thermostable 2-D layered Zn(II) compound, chemical terms are written as [Zn(3-pysa)2(H2O)2]n (1, 3-Hpysa = 3-pyridinesulfonic acid), has been generated from the solvothermal reactions of 3-Hpysa and Zn(NO3)2·6H2O. Its single crystal analysis was implemented via the single crystal X-ray diffraction analysis together with the powder X-ray diffraction, elemental analysis and thermogravimetric analysis. The crystal framework is of monoclinic P21/n space group and its crystal cell figures: a = 7.7499(5), b = 10.9923(6), c = 8.3430(5) Å, α = 90, β = 96.924(6), γ = 90°, V = 705.55(7) Å3, Z = 4. The 2D layers were finally combined to a 3-D supramolecular conformation through intermolecular H-bonds existing between coordinated H2O molecules and sulfonate oxygen atoms from adjacent layer. Its practical role in pulpitis treatment was estimated and the relevant mechanism was studied in the meantime. 相似文献