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Previously published experimental viscosity data at low density, originally obtained using all-quartz oscillating-disk viscometers for R134a and six vapors of aromatic hydrocarbons in the temperature range between 297 K and 631 K at most, were re-evaluated after an improved re-calibration. The relative combined expanded ($$k=2$$ k = 2 ) uncertainty of the re-evaluated data are 0.2 % near room temperature and increases to 0.3 % at higher temperatures. The re-evaluated data for R134a as well as for the vapors of mesitylene, durene, diphenyl, fluorobenzene, chlorobenzene, and p-dichlorobenzene were arranged in approximately isothermal groups and converted into quasi-isothermal viscosity data using a first-order Taylor series in temperature. Then, the data for R134a were evaluated by means of a series expansion truncated at first order to obtain the zero density and initial density viscosity coefficients, $$\eta ^{(0)}$$ η ( 0 ) and $$\eta ^{(1)}$$ η ( 1 ) . For the six aromatic vapors, the Rainwater–Friend theory for the initial density dependence of the viscosity was used to derive $$\eta ^{(0)}$$ η ( 0 ) values. Finally, reliable $$\eta ^{(0)}$$ η ( 0 ) and also $$\eta ^{(1)}$$ η ( 1 ) values for R134a were selected as reference values in the measured temperature range to be applied when generating a new viscosity formulation.

Direct exfoliation of layered zeolites into solutions of monolayers has remained unresolved since the 1990s. Recently, zeolite MCM-56 with the MWW topology (layers denoted mww) has been exfoliated directly in high yield by soft-chemical treatment with tetrabutylammonium hydroxide (TBAOH). This has enabled preparation of zeolite-based hierarchical materials and intimate composites with other active species that are unimaginable via the conventional solid-state routes. The extension to other frameworks, which provides broader benefits, diversified activity, and functionality, is not routine and requires finding suitable synthesis formulations, viz. compositions and conditions, of the layered zeolites themselves. This article reports exfoliation and characterization of layers with ferrierite-related structure, denoted bifer, having rectangular lattice constants like those of the FER and CDO zeolites, and thickness of approximately 2 nm, which is twice that of the so-called fer layer. Several techniques were combined to prove the exfoliation, supported by simulations: AFM; in-plane, in situ, and powder X-ray diffraction; TEM; and SAED. The results confirmed (i) the structure and crystallinity of the layers without unequivocal differentiation between the FER and CDO topologies and (ii) uniform thickness in solution (monodispersity), ruling out significant multilayered particles and other impurities. The bifer layers are zeolitic with Bronsted acid sites, demonstrated catalytic activity in the alkylation of mesitylene with benzyl alcohol, and intralayer pores visible in TEM. The practical benefits are demonstrated by the preparation of unprecedented intimately mixed zeolite composites with the mww, with activity greater than the sum of the components despite high content of inert silica as pillars.

Secondary electrospray ionization coupled with high resolution mass spectrometry (SESI-HRMS) is a direct mass spectrometry technique, which can identify trace volatile organic compounds (VOCs) in real time without sample pretreatment and chromatographic separation. SESI-HRMS has been successfully applied in multiple applications, including breath analysis, animals and plants VOCs emissions, analysis of headspace of cell cultures and indoor and outdoor air. The range of areas where the technique can potentially have a substantial impact is very broad. However, one critical aspect that requires further development to consolidate the technique is absolute quantification. Therefore, in this study we aim to develop a quantitative method for eight representative VOCs, including ketones (acetone, 2-butanone and 2-pentanone), alkenes (isoprene and α-terpinene) and aromatics (toluene, styrene and mesitylene). The mass spectrometric platform includes a commercial SESI source hyphenated with a Q-Exactive hybrid quadrupole Orbitrap high resolution mass spectrometer. Within the concentration range of 0–100 ppbv studied, the optimal coefficient of determination for linear regression (R2 = 0.993–0.999) between signal intensity and concentration is obtained in the range of 0–10 ppbv for all eight VOCs. The detection limits range between 3 (2-Pentanone) and 15 (Acetone) pptv. The intra-day (n = 10) and inter-day (n = 30) coefficients of variation (CV) are ≤ 6% and ≤10%, respectively. Finally the method is applied for the fast evaluation (

—The condensation of acetone under supercritical conditions was studied at different temperatures, pressures, and densities in a static mode. The high yield of mesitylene under the given conditions and its easy isolation from the reaction mixture made it possible to propose a new method for its preparation.

Bis(1,3,5-trimethylbenzene)gallium(I) tetra­chloridoaluminate(III), [(1,3,5-(CH3)3C6H3)2Ga][AlCl4] (1), bis(1,3,5-trimethylbenzene)gallium(I) tetrabromido­aluminate(III), [(1,3,5-(CH3)3C6H3)2Ga][AlBr4] (2) and (1,3,5-trimethylbenzene)gallium(I) tetraiodidoaluminate(III), [1,3,5-(CH3)3C6H3Ga][AlI4] (3) were synthesized from the corresponding subvalent GaI/AlIII mixed metal halides and characterized via C,H analysis, Raman spectroscopy, X-ray powder diffraction and X-ray single crystal diffraction. Compound 1 crystallizes in the noncentrosymmetric monoclinic space group Cc isotypic to [(1,3,5-(CH3)3C6H3)2Ga][GaCl4]. For 2 and 3 the monoclinic space group P21/n is found, however, they are neither isotypic nor homotypic. While 2 is isotypic to [(1,3,5-(CH3)3C6H3)2In][InBr4], 3 establishes a new structure type. In the solids of all three title compounds coordination polymeric chains are found, in 1 and 2 built up from bis(arene)-coordinated, in 3 from mono(arene)-coordinated Ga+ ions and the corresponding AlX 4 − anions in a 1κCl:2κCl′ (1), 1κCl,Cl′:2κCl″ (2) or 1κCl,Cl′:2κCl″:3κCl‴ (3) bridging mode. Taking into account the weaker coordinating character of the AlCl4 − as compared to the AlBr4 − anion, in line with expectations the number of gallium halogen contacts is increased and the strength of the π-arene bonding is reduced in the bromide 2 as compared to the chloride 1. Finally, with the even more strongly coordinating AlI4 − anion the arene coordination is limited to one molecule. Considering mesitylene complexes of gallium, the formation of a mono(arene) complex is unprecedented and even considering group 13 elements in general, the formation of a mono(mesitylene) complex like 3 is unusual. Furthermore, compound 3 is the first structurally characterized arene solvate of a main group metal tetraiodidometallate.

Reducing the nitrogen-containing compounds (NCCs) in fuel oils to ultralow level is essential for preventing the oil refining catalysts from being poisoned and for protecting the environment. Adsorptive denitrogenation is proved to be an effective mean to reduce the NCCs content. Herein, a series of N-doped porous carbons (NDPCs) in possession of proper pore structures, large surface area and moderate N species, which is verified through a series of characterization, are synthesized on the basis of the precursor copolymerized between 2,4,6-tris(chloromethyl)mesitylene and ethylenediamine. The NDPC-700 produced from the copolymer carbonization at 700 °C exhibits a record high adsorptive capacity of 7.35 mmol·g−1 for indole in the model oils, and the stable performance on the NCC adsorption is observed after 10 cycles of regeneration and reusage. The excellent adsorption capacity is attributed to the synergistic effect between porosities and N-containing sites. Moreover, the first-principle simulation proves that the N species, in particular the N-5 species, is helpful to the improvement of the adsorption capacity for indole.

N-doped porous carbons (NPCs) are characterized by well-developed porosity and N-doped active sites, which makes them suitable for CO2 capture. However, their application in practice is obstructed by the relatively low N-doped content and unsatisfactory adsorption capacity. Herein, we report the synthesis of NPCs through the rational design of the precursor NUT-21 (NUT means Nanjing Tech University) with a record-high N content (up to 46.16%, wt). The NUT-21 was fabricated by the polymerization of two simple monomers of 2,4,6-tris(bromomethyl)mesitylene and 3,5-diamino-1,2,4-triazole with an unusually high N content of 70.67% (wt). With the carbonization of NUT-21 at different temperatures (500, 600, and 700 °C, respectively), a series of NPCs possessing various porosity and N contents are produced, successfully. For the NPC generated at 600 °C, the N content can reach 7.41% (wt), the surface area is 2208 m2/g, the micropore volume is 0.791 cm3/g, and the CO2 capacity is up to 8.3 mmol/g at 273 K and 1 bar, which is much higher than those of benchmarks including 13X zeolite (4.1 mmol/g) and activated carbon (2.8 mmol/g), and most carbon-based adsorbents reported till now. It was proved in our previous studies that the ultrahigh N content of the precursor was beneficial for both the formation of developed porosity and the generation of abundant N-doped sites, which can give rise to superior capacity and selectivity of CO2 capture. The NPCs obtained may offer to be highly promising candidates for CO2 separation from gas mixtures including natural gas and flue gas.

Deprotonation of 1,1'-bis(ortho-carborane) with nBuLi in THF followed by reaction with [RuCl2(p-cymene)]2 affords, in addition to the known compound [Ru(κ3-2,2',3'-{1-(1'-closo-1',2'-C2B10H10)-closo-1,2-C2B10H10)}(p-cymene)] (I), a small amount of a new species, [Ru(κ3-2,2',11'-{1-(7'-nido-7',8'-C2B9H11)-closo-1,2-C2B10H10)}(p-cymene)] (1a), with two B-agostic B-H⇀Ru bonds, making the bis(carborane) unit a closo-nido-X(C)L2 ligand, a previously unreported bonding mode. Similar species were also formed with arene = benzene (1b), mesitylene (1c), and hexamethylbenzene (1d), although in the last two cases the metallacarborane-carborane species [1-(1'-closo-1',2'-C2B10H11)-3-(arene)-closo-3,1,2-RuC2B9H10)], 2c and 2d, were also isolated. With the bis(ortho-carborane) transfer reagent [Mg(κ2-2,2'-{1-(1'-closo-1',2'-C2B10H10)-closo-1,2-C2B10H10)}(DME)2], the target compounds [Ru(κ3-2,2',3'-{1-(1'-closo-1',2'-C2B10H10)-closo-1,2-C2B10H10)}(arene)], 4b and 4d, were prepared in reasonable-to-good yields, although for arene = benzene and mesitylene small amounts of the unique paramagnetic species [{Ru(arene)}2(μ-Cl)(μ-κ4-2,2',3,3'-{1-(1'-closo-1',2'-C2B10H9)-closo-1,2-C2B10H9})], 3b and 3c, were also formed. In compounds 3, the bis(carborane) acts as a closo-closo-X4(C,C',B,B') ligand to the Ru2 unit. In I, 4b, and 4d, the B-agostic B-H⇀Ru bond is readily cleaved by MeCN, affording compounds [Ru(κ2-2,2'-{1-(1'-closo-1',2'-C2B10H10)-closo-1,2-C2B10H10})(arene)(NCMe)] (5a, 5b, and 5d) and suggesting that I, 4b, and 4d could act as Lewis acid catalysts, which is subsequently shown to be the case for the Diels-Alder cycloaddition reactions between cyclopentadiene and methacrolein, ethylacrolein and E-crotonaldehyde. All new species were characterized by multinuclear NMR spectroscopy and 1a, 1c, 1d, 2c, 2d, 3b, 3c, 4b, 4d, 5a, 5b, and 5d were also characterized crystallographically.

Treatment of bis(mesitylene)niobium(0) with 6–7 equivalents of 2,6-dimethylphenyl isocyanide (CNXyl) affords two products with the empirical formula Nb(CNXyl) n (n = 7 or 6), which have been shown to be the diamagnetic dimers bis[μ-N,N′,N′′,N′′′-tetrakis(2,6-dimethylphenyl)squaramidinato(2−)]bis[pentakis(2,6-dimethylphenyl isocyanide)niobium(I)], [Nb2(C9H9N)10(C36H36N4)] or [Nb(CNXyl)5]2[μ-C4(NXyl)4]·xSolvent, 1, and bis[μ-N,N′,N′′,N′′′-tetrakis(2,6-dimethylphenyl)squaramidinato(2−)]bis[tetrakis(2,6-dimethylphenyl isocyanide)niobium(I)] tetrahydrofuran trisolvate, [Nb2(C9H9N)8(C36H36N4)]·3C4H8O or [Nb(CNXyl)4]2[μ-C4(NXyl)4]·3THF (THF = tetrahydrofuran), 2. Each contains NbI bound to either five or four terminal isocyanides, respectively, and to an unprecedented bridging tetraarylsquaramidinate(2−) unit, coordinated as a bidentate ligand to each niobium center, symmetrically due to the crystallographic inversion center that coincides with the centroid of the central C4 unit. Thus, in the presence of CNXyl, the bis(mesitylene)niobium(0) is oxidized to niobium(I), resulting in the facile loss of both mesitylene groups and the reductive coupling of two CNXyl groups per niobium to provide the first examples of tetraarylsquaramidinate(2−) ligands, [cyclo-C4N4Ar4]2−, coordinated to metals. In contrast, bis(mesitylene)niobium(0) reacts with the more crowded 2,6-diisopropylphenyl isocyanide (CNDipp) to afford the paramagnetic monomer hexakis(2,6-diisopropylphenyl isocyanide)niobium(0), [Nb(C13H17N)6] or Nb(CNDipp)6, 3, the first zero-valent niobium isocyanide analog of the highly unstable Nb(CO)6, which is presently only known to exist in an argon matrix at 4.2 K.

We reported a perfect strategy for the fabrication of Cu-encapsulated hierarchical MEL zeolites by a simple post-desilication–recrystallization strategy. The Cu-encapsulated hierarchical MEL zeolit...

Reactions of ortho-fluorinated anilines with stoichiometric Ti(NMe2)4 in mesitylene (typically for 23 h at 120 °C) afforded moderate to high yields of the corresponding N,N-dimethyl-1,2-phenylenediamine derivatives resulting from defluoroamination of a fluorine atom vicinal to the NH2 of the starting aniline. Reactivity increases with additional ring fluorination in general accordance with established regiochemical (activating and deactivating) trends.

Because of their high stability, abundant porosity, and tailorable surface properties, N-doped porous carbons (NPCs) have played a crucial part in CO2 capture. Development of an efficient and low-cost method to fabricate NPCs remains a significant challenge. Herein, we report for the first time the preparation of NPCs through the rational design of the N-enriched polymer NUT-20-EDA (NUT, Nanjing Tech University; EDA, ethylenediamine) as the precursor. The NUT-20-EDA was obtained by polymerization of two simple monomers of mesitylene and formaldehyde dimethyl acetal, followed by post-synthetic ammonification. Through carbonization at temperatures ranging from 600 °C to 800 °C, NPCs with different porosity and N contents are fabricated, successfully. The reference porous carbons (rPCs) are also synthesized based on the polymer NUT-20 without post-synthetic ammonification. For the representative sample generated at 700 °C (NPC-700), the surface area is up to 1852 m2/g, which is much larger than its counterpart rPC-700 (1324 m2/g). Moreover, the CO2 uptake of NPC-700 (7.1 mmol/g at 0 °C and 1 bar) is higher than that of rPC-700 (5.9 mmol/g), and also superior to those of many benchmarks reported, including 13X zeolite (4.1 mmol/g) and activated carbon (2.8 mmol/g). Therefore, it is proved that, as a pore-foaming agent during the carbonization, the amino groups incorporated play a significant role in the formation of abundant porosity of the NPCs, which is one of the crucial factors for CO2 adsorption, and the N-species doped in NPCs can work as the CO2-philic sites to enhance the CO2 capture.

International audience; The special case of the stacking of trihalogeno mesitylene (TXM) molecules has been investigated. Below 300 K, these molecules lead to needle shaped crystals in a triclinic arrangement. Thanks to DFT computations and an empirical atom-atom interaction model this packing mode has been rationalized. Aggregates of TXM molecules differently packed have been considered, namely dimers and trimers of type A, the molecules being piled one over the other along the axis a, and dimers B and trimers B, the molecules lying in the same bc plane. From the computations, it appears that the stabilizing energy of formation of a dimer of two molecules piled along a is several times larger than the energy gain obtained from the formation of a dimer of two neighbors in the bc plane. It has also been found that the energy of formation of a trimer of type A is approximately twice the energy of formation of a dimer A, so that an additive rule occurs. These conclusions are in perfect agreement with the experimental observations of the shape of the crystals obtained by crystallization from a super-saturated solution of TXM in an organic solvent long needles with TXM molecules stacked along the axis a have always been obtained and never thin plate-like crystals. © 2019 Elsevier B.V.

A new heterogeneous polymer supported solid phase oxovanadium(IV) catalyst was synthesized successfully. The designed catalyst furnished excellent results in the oxidation reactions of various aromatic alkanes, e.g. toluene, para-xylene, mesitylene. The polymer supported vanadium complex was proved also an efficient catalyst for the oxidation of aromatic alkenes, like substituted styrenes, trans-stilbene, etc. under mild reaction conditions. The supported catalyst was nicely elucidated by SEM-EDAX, TGA, FT-IR and UV–Vis spectral analysis. The catalytic activity was tested in the presence of an environment-friendly oxidant, 30% aqueous H2O2 during the oxidation of broad range of substrates. Another important fact is that the designed oxovanadium(IV) catalyst is heterogeneous in nature. Moreover, the newly synthesized oxovanadium(IV) complex exhibited a notable recoverability and it could be recycled up to six runs devoid of any prominent reduction in catalytic behavior.

An efficient protocol for C–H condensation of hypervalent iodine compounds toward arenes in fluoroalcohols has been applied to the recyclable preparation of mesityl iodonium(III) salts. The electrophilicities of [hydroxy(tosyloxy)iodo]mesitylene (MesI(OH)OTs) and iodomesitylene diacetate (MesI(OAc)2) are suitably enhanced in 2,2,2-trifluoroethanol. A series of nucleophilic aromatic compounds react smoothly with MesI(OH)OTs and MesI(OAc)2 or in situ hypervalent iodine(III) species, generated from iodomesitylene, to provide the target mesityl iodonium(III) salts in good yields at room temperature with broad functional group tolerance. This C–H condensation strategy merits high para-regioselectivities during the diaryliodonium(III) salt formation, but the major limitation in the case of low-reactive aromatic substrates is byproduct formation resulting from the self-condensation of the nucleophilic mesitylene ring in MesI(OH)OTs and MesI(OAc)2.

Two-dimensional (2D) layered zeolites are new forms of 3D zeolite frameworks. They can be pillared to form more open porous structures with increased access for reactants that are too big for the micropores of zeolites. The current pillaring procedure, however, requires intercalation of pillaring precursors by dispersing 2D zeolite in an alkoxide liquid and hydrolizing entrapped alkoxide to form inorganic oxide pillars in an aqueous alkaline solution. Both steps use excess solvents, generate significant waste, and require multiple synthesis and separation steps. Here we report a vapor-phase pillarization (VPP) process to produce pillared zeolites from 2D layered zeolite structures. The VPP process has ∼100% efficiency of alkoxide usage in the intercalation step, requires less (and, in some cases, zero) water addition in the hydrolysis step, does not require separation for product recovery, and generates no liquid waste. Furthermore, synthesis of pillared zeolites via the VPP process can be accomplished within a single apparatus with one-time operation. The pillared zeolite prepared by the VPP method preserved the zeolitic layered structure as well as acidity and showed enhancement in catalytic alkylation of mesitylene with benzyl alcohol compared to 2D layered zeolite without pillarization treatment.

We reported a strategy to synthesize MFI zeolites with tunable properties by tailoring organic structure-directing agents (OSDAs) under the hydrothermal conditions. The tailored surfactants were obtained by tuning the structure of Gemini-type Cph-10-6-6 and Bola-type BCph-10-6-6, including alkyl tail chains, ammonium groups and alkyl middle chains. The textural property, morphology and acidity of resulting MFI zeolites were characterized by a complementary combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption isotherms and FTIR spectra of pyridine adsorption. Moreover, the correlation between the OSDAs’ composition and the inorganic precursor in the fabrication of zeolite framework was investigated by DFT calculations in this study. The catalytic performance of the resulting MFI samples was investigated by the alkylation of mesitylene with benzyl alcohol. The results revealed that the OSDAs without ammonium groups only leaded to form the micro-structure of zeolites, but the OSDAs with ammonium groups can induce the formation of micro- and meso-structure simultaneously, regardless the OSDAs ended with or without alkyl tail chains. In addition, the resulting MFI zeolites showed an improved catalytic activity in alkylation of mesitylene with benzyl alcohol due to the enhanced pore accessibility, the acidity (Bronsted/Lewis) controlled the activation of benzyl alcohol, and the ratio of external surface area (Sext/SBET) governed the selectivity of alkylation reaction. As a result, tailoring the structure of OSDAs can pick another strategy to synthesize MFI zeolites with tunable zeolite structure and catalytic performance.

Separation of 1-butanol from the model fermentation broth (98 wt% water + 2 wt% ABE, acetone: 1-butanol: ethanol = 3: 6: 1) using liquid-liquid extraction (LLE) was investigated in this paper. This investigation involved multi-scale simulations from ab initio calculation to process simulation. Firstly, suitable extractant was screened from ionic liquids (ILs) combined of 30 anions and 40 cations using conductor-like screening model for real solvent (COSMO-RS) model. Meanwhile, the equilibrium experiment of the system ABE solution+selected IL was conducted to verify the screening result. From the screening, [HMIM][FEP] was found to be an optimal extractant and the experimental data confirmed this screening result with a deviation of 3.54%. The continuous hybrid process consisting of extraction and distillation section with the selected IL was also simulated and compared with a referenced process selecting mesitylene as extractant using Aspen Plus to investigate the performance of IL in real industry. The simulated results showed that a higher mass purities and yields of acetone (≥99.5 wt%), ethanol (≥99.5 wt%) and 1-butanol (≥99.9 wt%) could be obtained with much lower capital cost and energy consumption when the extractant was compared from [HMIM][FEP] to mesitylene. The extractant consumption and the energy consumption could lower 10% and 4.4% in total, respectively. The ab initio calculation enabled a deep insight on the mechanism of IL in extraction. Obviously, the results uncovered by the ab initio calculation showed that interaction between IL and 1-butanol was much stronger than mesitylene.

It has been found that catalytic deoxygenation of triglycerides is a viable pathway for obtaining renewable liquid fuels to contribute to meet the global energy demand. In this study, SBA-15 mesoporous silica was synthesized in a pure form and modified with mesitylene (TMB) as a swelling molecule (SBA15-TMB). Catalysts with 0.5, 1.5 and 3.0 wt% Pd were synthesized and tested by deoxygenation of stearic acid (SA), obtaining initial conversions of 68–98% that decreased to 36–73% after 6 h time-on-stream. The most abundant product was n-heptadecane, with a selectivity of ~ 90%. The most active catalyst evaluated with SA was 3.0 wt% Pd over unmodified SBA-15 (30Pd/SBA-15). Subsequently, fresh and regenerated 30Pd/SBA-15 catalysts were tested with waste cooking oil (WCO) feed, obtaining conversions of 74 and 72%, respectively, but the fresh catalyst allowed a better oxygen removal (91%. Additionally, commercial Pd(10wt %)/C catalyst was evaluated, obtaining results comparable to those for the regenerated 30Pd/SBA-15 catalyst. The main WCO reaction product for all catalysts was a diesel fraction (C12-C21), and the quality of the products was not very different, following the order: Pd(10wt %)/C > 3.0Pd/SBA-15-regenerated > 3.0Pd/SBA-15-fresh. The results obtained indicate that shynthetized catalysts of this study are promising for obtaining renewable diesel from low-cost feeds while using low hydrogen consumption.

Mesitylene, a representative heavy carbon by-product in the course of C1 chemical downstream processes, is proposed to be employed in this study, as the initial material to synthesize the porous carbons that have played a crucial part in the adsorptive carbon capture process but are generally made from natural carbon resources, instead of fed to the traditional refining process such as hydroprocessing. Based on molecular dynamics calculation, it is proved that once the mesitylene monomers are linked by the flexible methylene groups, the generated polymer can closely mimic the lignin macromolecular behaviors in terms of spatial configuration and atomic thermal motions, which gifts the great potential of the mesitylene-based polymer as applicable a precursor of porous carbon as the biomass-based material. The experimental facts further demonstrate that the porous carbons produced through the routine carbonization of the mesitylene-based polymer can possess desired textural peculiarities, in particular the finely developed micropores that give rise to perfect capacity and selectivity of CO2 capture, of which underlying mechanism is revealed by the first-principle calculation. The porous carbon generated at 700 °C can reach the CO2 capture capacity of 6.16 mmol g−1 at 0 °C and 1 bar, which is much higher than many benchmark materials reported, including some biomass-based porous carbons (2.8 mmol g−1, at 0 °C and 1 bar).

The use of silver trifluoromethanesulfonate (silver triflate, AgOTf) as a halide abstraction reagent is pervasive in organometallic chemistry. However, recent reports suggest a “hidden” Bronsted acid lurks within it that may catalyze purported metal-based catalysis. Presented herein are new reactions that are either catalyzed or promoted by the “hidden” acid, generated upon silver triflate degradation. 1-Phenylethanol dehydrates to styrene (1) upon reaction with AgOTf at 90 °C over 24 h, which slowly coverts to the vinyl hydrovinylation product (E)-1,3-diphenyl-1-butene, (2, 64%) over several days. While dehydration was observed with a number of benzylic alcohols to yield Zaitsev selective olefins, only 1-phenylethanol affords vinyl hydrovinylation products. Dehydration was not observed for primary and secondary alcohols, suggesting an acid catalyzed E1elimination reaction mechanism is at play. The degradation of silver triflate was found to be the source of the “hidden” Bronsted acid, which demonstrated a dependence on the presence of light and oxygen. In the absence of light and oxygen, dehydration of 1-phenylethanol was severely stunted and 2 is not formed, but instead the ether product, oxy-bis(ethane-1,1-diyl)dibenzene (3), is afforded. The mesitylene internal standard also reacts with the in situ formed styrene to produce 2-(1-phenylethyl)mesitylene (4) through acid catalyzed electrophilic aromatic substitution. These reactions were monitored (products characterized) by GC-MS and/or 1H NMR spectroscopic methods. We present herein the details of these reactions and our characterization methods.

Meso- and microporous ZSM-5 zeolites were synthesized through combination of the tetrapropylammonium hydroxide (TPAOH) and single quaternary ammonium surfactant (Cph–ph–10–6) as dual templates. The structure-directing ability of Cph–ph–10–6 and TPA+ was investigated by density functional theory (DFT) calculation. By tuning the molar ratios of Cph–ph–10–6/TPAOH from 5/0 to 5/8, the structure-directing effects between Cph–ph–10–6 and TPA+ could be systematically modulated, resulting in the morphology of the mesoporous ZSM-5 zeolites changed from ultrathin nanosheets, through splint-like nanosheets, to condensed packing plates. In addition, the hierarchical ZSM-5 zeolites exhibited a greater catalytic activity in alkylation of mesitylene with benzyl alcohol compared with conventional ZSM-5 zeolite. The fine control of meso- and microporous structures of ZSM-5 zeolites by a simple one-step dual template synthesis approach allows the design of the desired catalysts for a green and sustainable future.

Molecular and crystal structure of 2,4,6-tris(4-hydroxy-3,5-di-tert-butylphenylthio)methylbenzene and 2,4,6-tris(4-hydroxy-3,5-di-tert-butylphenylthio)-1,3,5-triazine molecules exhibiting antioxidant activity is studied. These molecules have asymmetric conformations, in contrast to previously studied and similarly substituted mesitylene and resorcinol molecules, which have a “basket” conformation in crystals. One of the substituents appears on the opposite side of the plane of the central aromatic ring. Unlike mesitylene and resorcinol derivatives, which do not form hydrogen bonds in crystals due to the shielding of hydroxyl groups by tert-butyl substituents, the crystals studied exhibit intermolecular O-H…S hydrogen bonds.

The thermal decomposition of N-nitrosoamides has experimentally been demonstrated to depend on several factors, such as temperature, solvent and the substituents on the substrate. Consequently, a number of reaction mechanisms have been proposed for this process in the literature. In this work, we present a comprehensive computational investigation in which we examine the detailed reaction mechanisms for two N-nitrosoamides (with aliphatic and aromatic substituents) in two different solvents (mesitylene and methanol). It is shown that the reaction mechanism can change dramatically with the nature of the substrate and the choice of solvent. Importantly, it is found that the polar solvent stabilizes ion-pairs that are unstable in the non-polar solvent, which can play a key role in the mechanism.

Stereospecific cis-1,4 polymerization of 1,3 butadiene is carried out by using CpTiCl3/MAO and Cp*TiCl3/MAO catalysts in solvents (mesitylene, toluene, benzene, chlorobenzene, m-chlorobenzene, hexafluorobenzene) having different nucleophilicity. The influence of nucleophilicity of used solvent on activity and selectivity of the two considered catalytic systems is evaluated. Catalyst activity is strongly affected by used solvent, while polymer microstructure remains almost unchanged. The formation of a labile specie anti-η3-π-butenyl-Ti coordinated to solvent molecule, able to increase the rate of polymerization reaction, is hypothesized. The effect of two different external electron donors, N(C2H5)3 and P(C6H5)3, in the polymerization environment on activity and selectivity of the two considered catalytic systems is also investigated. Both N(C2H5)3 and P(C6H5)3 induce a sweeping decrease of catalyst activity, but do not cause changes in polymer microstructures.

Efficient syntheses of four derivatives G2–G5 of Gabapentin (G1) have been achieved. The structures of targeted compounds were investigated by elemental analysis, FT-IR, and 1H-NMR spectroscopic method. Crystal structures of G2 and G4 determined by single crystal X-ray diffraction method are also described. In G2 the molecules are stacked over each other in the form of layers and adjacent layers run parallel to each other. Intermolecular hydrogen bonding and van der Waals interactions are responsible for building the molecular assembly and packing of molecules in the unit. In G4, the molecules are arranged in parallel sheets formed by inter-molecular hydrogen bonds. The proposed synthetic route has high impact due to its simple reaction conditions of room temperature, water as a green solvent and short time to accomplish the reaction.

Compounds {[Ba3(tpmm)(H2O)15]·5H2O}n (1) and {[Ba6(tpmm)2(H2O)22]·15H2O}n (2) were obtained through reactants slowly diffusion of barium acetate (Ba(CH3COO)2) and 2,4,6-tris(phosphorylmethyl)mesitylene (H6tpmm) at room temperature in H2O/THF/MeOH media without and with the addition of pyrazine (pz), respectively. Single-crystal X-ray structure analysis shows that compound 1 features a two-dimensional (2D) layer structure, with an I1O1 connectivity, in which the one-dimensional (1D) inorganic Ba−O−Ba double-stranded ribbon-like chains are cross-linked by the cis,cis,cis-configured μ3-tpmm6− anions. Compound 2 has also a 2D layer structure but with an I2O0 connectivity, in which the 2D inorganic Ba−O−Ba layer is capped by the cis,cis,cis-configured μ4- and μ3-tpmm6− anions. Of interest, in 2 there are significant cation−π interactions between the Ba2+ ion and the phenyl core of the μ4-tpmm6− anion. Compounds 1 and 2 both display a high thermal stability approaching to 402 °C and 545 °C, respectively, and emit three ligand-based emission bands in the solid-state at room temperature.

Domain size, phase purity, and the interpenetrating network within the active layer of all-polymer solar cells (all-PSCs) are crucial for efficient charge generation and carrier transport. However, it is a great challenge to decrease domain size and enhance phase purity simultaneously because of the energetically disfavoring polymer–polymer mixing and chain entanglement. In this work, we manipulated the domain size and phase purity of J51:N2200 blends by promoting their solution ordered aggregation and the confinement of acceptor N2200 to J51 during phase separation. Thus, three solvents, chloroform (CF), mesitylene (Mes), and cyclopentyl methyl ether (CPME), were selected. The solubility of J51 and N2200 in these three solvents decreases and solubility differences between J51 and N2200 increase gradually. Among these three solvents, only in CPME solution does N2200 possess ordered structures, which reduces the nucleation barrier to increase nucleation density and boost the template effect of N2200. During phase separation, the ordered aggregation of N2200 dominates solid–liquid phase separation and has a confinement effect of J51. Thus, the blend films cast from CPME have fine-scale phase separation in contrast to the films derived from CF. In addition, the “memory” effect of ordered aggregations transferred to films can enforce the order of blend films. As a result, the blend film with small domain size (≈21 nm), interpenetrating network structure, and a higher degree of crystallinity was obtained by processing using the green solvent CPME. The improved morphology facilitated the charge-generating process and carrier transport, resulting in a higher short-circuit current (Jsc), fill factor (FF), and power conversion efficiency (PCE).

As-cast polymer solar cells without any additive and pre- or post-treatments principally have high compatibility with mass production technologies, and efforts in achieving higher efficiencies are typically promoted by engineering new donor and acceptor materials. In this study, a binary solvent processing approach using chloroform (CF), as a good low boiling point solvent for both the donor polymer PTQ10 and the non-fullerene acceptor IT-4Cl, and mesitylene (MES), as a semi-orthogonal co-solvent with relatively high boiling point and weak solubility to the acceptor, is explored. Due to the selective orthogonality of MES to the IT-4Cl acceptor, an optimized morphology has been realized for the as-cast device based on the PTQ10:IT-4Cl blend, which leads to a simultaneous improvement in the open-circuit voltage, short-circuit current, and fill factor, finally achieving a high as-cast efficiency of over 13%. Furthermore, the as-cast devices fabricated with this binary solvent system exhibit good air stability and great accessibility in large area cells. Our findings provide an alternative guideline for the optimization of as-cast polymer solar cells.

Cationic β-diketiminate Mg complexes with the bulky tBuBDI ligand and the weakly coordinating anion B(C6F5)4− have been prepared by the reaction of (tBuBDI)MgnBu with [Ph3C]+[B(C6F5)4]−; tBuBDI = CH[C(tBu)N-Dipp]2 and Dipp = 2,6-diisopropylphenyl. Their structures are compared to the previously reported cationic (MeBDI)Mg+ complexes; MeBDI = CH[C(Me)N-Dipp]2. Crystallization of [(tBuBDI)Mg]+[B(C6F5)4]− from chlorobenzene gave a unique (tBuBDI)Mg+·ClC6H5 cation with a rather short Mg⋯Cl and consequently long C–Cl bond. Crystallization from chlorobenzene/arene solvent mixtures gave (tBuBDI)Mg+·arene complexes (arene = benzene, toluene, m-xylene) but in the presence of mesitylene the chlorobenzene complex was formed. Due to the greater shielding of the metal, none of these complexes display Mg⋯(F5C6)4B− interactions. Crystal structures of the arene complexes show in all cases η2-coordination of the arene ligands. Ring slippage from a more favorable η2-coordination can be explained by the steric bulk of the tBuBDI ligand. The smaller arenes, benzene and toluene, also bind to (tBuBDI)Mg+ in bromobenzene solution. The Lewis acidity of these cationic Mg complexes was determined by the Gutmann–Beckett test. The acceptor number for (tBuBDI)Mg+ (AN = 76.0) is substantially higher than that estimated for (MeBDI)Mg+ (AN = 70.3). Calculation of the atomic NPA charges by DFT shows that the Mg2+ ion in (tBuBDI)Mg+ is slightly more positively charged than the metal in (MeBDI)Mg+, confirming its higher Lewis acidity. The lower benzene complexation energy calculated for (tBuBDI)Mg+versus (MeBDI)Mg+ is due to steric congestion of the metal in the (tBuBDI)Mg+ cation which allows only for Mg⋯(η1)C6H6 instead of Mg⋯(η6)C6H6 bonding. This ring slippage, however, results in a significant polarization of the electron density in the benzene ring, making it susceptible for nucleophilic attack.

We performed nonequilibrium molecular dynamics simulations of the chemical vapor deposition (CVD) of hydrocarbons on a precursor-activated carbon model with a slit-like pore (in silico CVD simulation) to explore design guidelines for the synthesis of high-performance carbon molecular sieves (CMSs) for air-separation purposes. The dependence of the CVD process on gas species was investigated using “united-atom” hydrocarbons mimicking ethylene, benzene, toluene, and mesitylene. The obtained CMS models were then used to evaluation the diffusion rate constants of O2 and N2 using the transition state theory. We also constructed idealized carbon pore structures that extracted the characteristics of the CMS models obtained via the in silico CVD simulations to understand the relation between the size and geometry of pore mouths, diffusion rate constants, and kinetic O2 selectivity. We found that most of the simulated results were supported by experimental evidence. Furthermore, we conclude that a high-performance CMS for air separation requires the development of thin amorphous carbon at the pore mouths of the precursor-activated carbon by CVD, which provides a single energy barrier for O2 diffusion and effectively prevents the formation of multiple energy barriers.

Carboxyl group functionalized hollow microporous organic nanospheres (HMONs-COOH) were successfully synthesized by hyper-crosslinking reaction between polylactide-b-polystyrene (PLA-b-PS) diblock copolymers and 2,4,6-tris(bromomethyl)mesitylene as well as subsequent alkaline KMnO4 oxidation. The synthesized HMONs-COOH possess the high special surface area, robust organic framework and hierarchically porous structure, which shows highly catalytic activity in the Friedel-Crafts alkylation of indole with aldehydes and outstanding adsorption efficiency toward cationic dyes.

Two simple unsymmetrical monometallic Ir(i) complexes with an N-heterocyclic carbene ligand and an analogous bimetallic Ir(i) complex were synthesised. These complexes were found to be extremely active catalysts for a range of C-X (X = N or O) and Si-N bond forming reactions involving alkyne and imine activation for dihydroalkoxylation, hydroamination and hydrosilylation reactions. These catalysts exhibited reaction rates far exceeding those of other Rh(i) and Ir(i) complexes previously reported. In addition, a small change to the ligand design (phenyl vs. mesityl) substantially affected both the reactivity and product selectivity of the catalyst. The Ir(i) complex bearing a mesitylene wingtip provided unprecedented regioselectivity in the dihydroalkoxylation reaction and a new kinetic product from the typical hydrosilylation protocol of 2-benyzlpyrroline to produce an N-silylaminoalkene. Our mechanistic studies indicated that this transformation proceeded via a dehydrogenative coupling mechanism.

Organic aromatic cold neutron moderators - like mesitylene ( C 9 H 12 ) - are often much more convenient to handle and to commission than cryogenic methane or ortho/para hydrogen moderators. Although this benefit comes at the cost of reduced brilliance, mesitylene moderators are suited to enable cold neutron applications at sources where a complex traditional cold moderator system is not feasible. Developing the Julich High Brilliance neutron Source (HBS) project, we have investigated the use of such a low-dimensional mesitylene moderator with MCNP and ANSYS simulations and validated the simulations with experiments at TU Dresden's AKR-2 reactor. Here we will document the feasibility, advantages and drawbacks of such a system and give an outlook on future optimization potentials.

Diltiazem, which is a calcium channel blocker, is involved in the formation of covalent organic frameworks (COFs) through the Schiff base reaction of tetrakis (4-aminophenyl)-porphine (TAPP) and dihydroxynaphthalene-dicarbaldehyde (DHNDC) and the next enol-to-keto tautomerization. The diltiazem-imprinted COFs (DICOFs) were optimally formed using Sc(OTf)3 as the catalyst, TAPP/DHNDC/diltiazem in a molar ratio of 2/3/4, N-methylpyrrolidone/mesitylene (v/v = 3/5) as the porogen, and a 1-h reaction with a high imprinting factor of 10.5 compared to the nonimprinted counterparts (NICOFs). The optimized DICOF exhibited a more amorphous XRD pattern, a larger surface area (1650 vs. 930 m2/g), a larger pore volume (1.33 vs. 0.75 cm3/g), and a finer porous SEM feature than NICOF. The selectivity of NICOF toward diltiazem and diazepam at 250 nM (α = 1.03, RSD = 1.3%) was smaller than the selectivity of DICOF (α = 2.94, RSD = 1.6%). The diltiazem samples (5.0–300 ng mL−1) dynamically quenched the fluorescence of 15 μg/mL DICOF in 50 mM phosphate buffer at pH 6.5 at 8.0 min equilibrium; thus, Stern−Volmer plots were linearly constructed for sensing diltiazem with an LOD of 3.4 ng mL−1 and an LOQ of 10.2 ng mL−1. According to the plots, 30 ng mL−1 diltiazem solutions that were diluted from 30 mg-specified tablets had an average measured concentration of 29.5 ng mL−1 (σ = 1.3% and n = 5). In addition to application as fluorescent sensors, DICOFs (30 mg) could be used as dispersive extractants to recover 95.2% of 0.6 ng mL−1 diltiazem from 25 mL phosphate buffer with quadruplicate uses of 0.5 mL methanol/acetic acid (v/v = 9/1) as the eluent. Langmuir and pseudo-second-order models were fitted to the isothermal and kinetic sorption mechanisms, respectively. The maximum sorption capacity of DICOF was ten times larger than that of NICOF (156 vs. 15.2 mg/g). The interday recoveries of 0.6 ng mL−1 spiked in 20-fold diluted human urine, and 60-fold diluted human serum were 93.2% and 90.6%, respectively.