Schematic representation of the growth mechanism of the oxygen-vacancy-stabilized tetragonal zirconia particles in the APPJ system.
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•We demonstrate a nonthermal atmospheric pressure ...plasma jet for powder production.•The one-particle-per-drop mechanism under the plasma region was proposed.•The controlled oxygen vacancy on stabilization of tetragonal zirconia was applied.•Defect engineering on oxide material via the APPJ method is achieved.•APPJ system is green, cost-effective, and time-saving for nanoparticle production.
This study presented a controlled oxygen vacancy formation on stabilization of tetragonal zirconia particles via a nonthermal atmospheric pressure plasma jet (APPJ) with varying the supplied power. The characteristic analyses based on X-ray diffraction, field emission scanning electron microscopy, high-resolution transmission electron microscopy (HR-TEM), Raman, ultraviolet–visible spectroscopy, and ultraviolet photoemission spectroscopy confirm the existence of oxygen vacancies in tetragonal zirconia particles. Production of oxygen vacancies in the prepared zirconia powder is related to the presence of surface defects by observing HR-TEM and further decreases the bandgap as indicated by optical characterization. Thus, it can be anticipated that the research of defect engineering is a promising way to improve the optoelectronic and photocatalytic performance of oxide material via the APPJ method.
Recently, copper(I) complexes having thermally activated delayed fluorescence (TADF) have attracted much attention. Here, a series of new neutral luminescent dinuclear copper(I) halide complexes with ...the chelating ligand, 1,2-bis(diphenylphosphino)-4,5-dimethylbenzene (dpmb) were synthesized, and their molecular structures and photophysical properties were investigated. They consist of halogen-bridged dinuclear structures, Cu(μ-X)dpmb2 (X=I (1), Br (2), Cl (3)). In the solid state, these complexes display intense blue–green photoluminescence with lifetimes in the microsecond regime (λmax=498–527nm; Φ=0.28–0.32; τ=2.5–12.5μs) at 298K. The emission of the complexes originate from the (σ+X)→π* transition, where σ is the σ bond between Cu and P and X is the halogen. The organic light-emitting devices (OLEDs) using complexes 1–3 as the dopant emitters exhibit bright green luminescence with current efficiencies of 32.9cdA−1 and maximum external quantum efficiencies of 10.1%.
•We report 3+2 cycloaddition reactions of alkyne with the ruthenium azido complex.•The stable triazolato and tetrazolato products obtained in all cases were N(2)-bound.•We report that during ...protonation of ruthenium azido complex, methylene insertion accidentally took place, to yield unusual boron-methylated product.•Their structures are elucidated by IR, NMR and X-ray crystallography.
Herein, we report on the reactivity of an Ru(II) azido complex allowing the facile synthesis of further interesting complexes. Starting from the parent chlorido complex (HN=CPh2)Ru−Cl {1, Ru = Tp(PPh3)Ru; Tp = HB(pz)3, pz = pyrazolyl)} the title complex (HN=CPh2)Ru−N3 (2) was obtained upon reaction with NaN3. The N(2)-bound 4,5-bis-(methoxycarbonyl)-1,2,3-triazolato complex (HN=CPh2)Ru−{N3C2(CO2Me)2} (3) was obtained from reaction of 2 with dimethyl acetylene dicarboxylate (DMAD). Protonation of 3 with HCl afforded the N-coordinated triazolato complex {HN3C2(CO2Me)2}Ru−Cl (4). Reaction of CS2 with 2 produced the thiocyanato complex (HN=CPh2)Ru−NCS (5). The Ru tetrazolato complex (HN=CPh2)Ru−N4CC(CN)=C(CN)2 (6) was prepared from 2 and tetracyanoethylene (TCNE). The reaction of 2 with HX gave the 17-electron Ru(III) complexes (Cl)Ru−X (7a, X = Cl; 7b, X = Br) and the Ru(II) complexes containing the methyl tris(pyrazolyl)borate ligand MeTp(PPh3)(HN=CPh2)Ru−X (8a, X = Cl; 8b, X = Br), as a result of an unusual methylene insertion into the B−H bond of the Tp ligand with the CH2Cl2 solvent as the assumed source for the methylene. The structures of 4, 5, 7a, 7b and 8b had been determined by X-ray diffraction analysis.
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Metal‐free dyes (MD1 to MD5) containing an anthracene/phenothiazine unit in the spacer have been synthesized. The conversion efficiency (7.13 %) of the dye‐sensitized solar cell using MD3 as the ...sensitizer reached approximately 85 % of the N719‐based standard cell (8.47 %). The cell efficiency (8.42 %) of MD3‐based dye‐sensitized solar cells (DSSCs) with addition of chenodeoxycholic acid is comparable with that of N719‐based standard cell. The MD3 water‐based DSSCs using a dual‐TEMPO (2,2,6,6‐tetramethylpiperidine‐N‐oxyl)/iodide electrolyte exhibited very promising cell performance of 4.96 % with an excellent Voc of 0.77 V.
DSSCs get wet: Metal‐free dyes containing an anthracene/phenothiazine unit in the spacer are synthesized. Aqueous dye‐sensitized solar cells using these sensitizers and a dual electrolyte that comprises 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) and imidazolium iodide exhibit promising light‐to‐electricity conversion efficiencies and excellent Voc values.
Treatment of the TpRu complex Tp(PPh3)2RuCl (Tp = HB(pz)3, pz = pyrazolyl) (1) with ethynylferrocene in MeOH gave the trimetallic alkenyl ketone complex Tp(PPh3)Ru{C(Fc) = CHC(O)CH2(Fc)} ...(Fc=(η5-C5H4)Fe(η5-C5H5)) (2). Intriguingly, a similar reaction was performed in the presence of NaOMe afforded the dimetallic acetylide complex Tp(PPh3)2Ru–CC-Fc (3). A number of new cationic vinylidene complexes Tp(PPh3)2Ru{ = CC(Fc)CH2R}+ 4a, R = CN; 4b, R = HCCH2; 4c, R = CHC(CH3)2; 4d, R = Ph have been prepared by electrophilic addition of organic halides to complex 3. The substitution reaction of 4a with pyrazole is followed by an intramolecular nucleophilic addition of the nitrogen atom at the α-carbon atom and removal of HI to afford the metallacyclic complex, Tp(PPh3)Ru(C3H3NN)CC(Fc) CH2CN (5a). All of the complexes are identified by spectroscopic methods as well as elementary analysis. The structure of 2 has been determined by X-ray diffraction analysis. Pathways for the synthesis of these compounds are proposed.
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•We reported new method for synthesis of di and tri-metallic complexes.•Reaction of TpRu complex with ethynylferrocene in MeOH was studied.•A number of new cationic vinylidene complexes have been prepared.•Their structures are elucidated by IR, NMR and X-ray crystallography.
Materials with non-linear optical (NLO) properties play an important role in the construction of electronic devices for optical communications, optical data processing and data storage. With this aim ...in mind, a Zn(II)-based metal-organic framework {Zn2(nica)2(bpy)1.5(H2O)×0.5(bpy)×3H2O}n (1), was synthesized using 4,4'-bipyridine (bpy) and a potentially bidentate ligand, 2-hydroxynicotinic acid (H2nica) with a salicylate binding moiety. A single-crystal X-ray diffraction analysis revealed that compound 1 crystallized in the orthorhombic space group Fdd2 and was composed of a three dimensional porous framework. Since Fdd2 belonged to a class of non-centrosymmetric space groups, we therefore investigated the non-linear optical behaviour of compound 1. Photoluminescence studies revealed that compound 1 exhibited a blue light emission with a maxima at 457 nm.
Treatment of the TpRu complex (PPh3)Ru-Cl (1, Ru = Tp( t BuNC)Ru) with an excess of sodium azide affords the yellow ruthenium azido complex (PPh3)Ru-N3 (2). The triazolato complexes (PPh3)Ru-N3C2(R)2 ...(3a, R = Me; 3b, R = Et) are synthesized via 3+2 cycloadditions of 2 with RO2CCCCO2R. Complete characterization of these triazolato complexes elucidates the structures and establishes the N(2)-bonding type of the addition products. Alkylation of 3a with organic bromides causes cleavage of the Ru–N bond and affords 1,4,5-trisubstituted triazoles. Moreover, addition of CS2 to 2 produces thermally unstable thiothiatriazolate (PPh3)Ru-N3CS(S) (5), which converts to the isothiocyanate complexes (PPh3)Ru-NCS (6) and ( t BuNC)Ru-NCS (7). Other reagents also react with 2, but the products do not result from 3+2 cycloadditions. Terminal alkynes undergo ligand substitution reactions rather than a 3+2 cycloaddition with 2 in the presence of H2O to produce the carbonyl complexes (CO)Ru-CH2R (8a, R = Ph; 8b, R = 4-CH3Ph) through ruthenium vinylidene intermediates. Reaction of 2 with H-CC-CMe2OH in MeOH gives the cationic Fischer carbene complex {(PPh3)RuC(OMe)-HCC(Me)2}+ (10). In contrast, reaction of H-CC-CH2CH2OH gives rise to the five-membered cyclic oxycarbene complex {(PPh3)RuC4H6O}+ (11). Several cationic imine complexes {( t BuNC)Ru-(NHCHR′)}+ (12a, R′ = H; 12b, R′ = CH3; 12c, R′ = Ph) are formed by the reaction of RCH2X with 2. If the reaction of 2 with CH3I is carried out at 35 °C for 24 h, ( t BuNC)Ru-I (13) could be isolated. Preliminary results on the catalytic activity of 2 are also presented. Complex 2 catalyzes cycloaddition of alkynes and benzyl azide to give the triazoles in organic and aqueous medium. The structures of 1, 2, 3a, 7, 8a, 10, 11, 12b, 12c, and 13 have been determined by X-ray diffraction analysis.
We describe a simple and efficient ruthenium-catalyzed reaction in which propargylic alcohol HCCC(Ph)2OH is split into carbon monoxide CO, formaldehyde H2CO and ketone (Ph)2CO via cleavage of ...carbon-carbon triple and single bonds. A plausible reaction mechanism is proposed on the basis of ruthenium vinyl and formyl intermediates
We describe a simple and efficient ruthenium-catalyzed reaction in which propargylic alcohol HCαCβ-Cγ(R1R2)OH is split into carbon monoxide CαO, formaldehyde H2CβO and ketone (R1R2)CγO via cleavage of carbon-carbon triple and single bonds. A plausible reaction mechanism is proposed on the basis of ruthenium vinyl and formyl intermediates. Display omitted
•We disclose the results of detailed catalytic and structural investigations on the reaction of propargylic alcohol with TpPPh3(HNCPh2)RuCl.•A number of new ruthenium complexes have been prepared.•A plausible reaction mechanism is proposed on the basis of ruthenium vinyl and formyl intermediates.•Their structures are elucidated by IR, NMR and X-ray crystallography.
The catalytic activity of a series of ruthenium azido complexes containing Tp ligands has been evaluated for the cycloaddition of terminal alkynes and azides to give selectively 1,5-disubstituted ...1,2,3-triazoles. The complex Tp(PPh3)(EtNH2)RuN3 (2, Tp = HB(pz)3, pz = pyrazolyl) was found to be an effective catalyst for the cycloaddition reactions. In the presence of complex 2, azides reacted with a range of terminal alkynes containing various functionalities to selectively produce 1,5-disubstituted 1,2,3-triazoles. Theoretical calculations support the proposed mechanism.
In the presence of complex Tp(PPh3)(EtNH2)RuN3 (2), azides reacted with a range of terminal alkynes containing various functionalities to selectively produce 1,5-disubstituted 1,2,3-triazoles. Theoretical calculations support the proposed mechanism. Display omitted
•We reported new method for synthesis of ruthenium azido complex.•Ruthenium azido complex catalyzes click reactions of some terminal alkynes HCCR and alkyl azide in organic and aqueous medium.•Their structures are elucidated by IR, NMR and X-ray crystallography.•Theoretical calculations support the proposed mechanism.
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