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1.
Crystal engineering, as a burgeoning technology, has been widely used to construct metalloporphyrins biomimetic catalysts. Herein, a bimetallic metal-organic framework (MOF) was constructed by 4-(4-carboxyphenyl)-1,2,4-triazole ligand, Co2+ and Zr4+ metal ions by solvothermal reaction(named PFC-88). A N,N-chelation site was found between the two adjacent ligands in PFC-88, consequently a porphyrin-like structure was obtained through chelating Fe3+ in this site by post-modification, named PFC-88-Fe. The result of a single crystal X-ray technology verified that Fe ions were successfully metalated in the N,N-chelation site of PFC-88, which is assisted by the X-ray absorption near-edge structure(XANES) spectra. An o-phenylenediamine oxidation reaction was applied to assessing the catalytic activity of PFC-88-Fe, in which the absorbance increases of phenazine-2,3-diamine at λ=418 nm were recorded by absorption spectroscopy in kinetic mode, exhibiting the application potential as a biomimetic catalyst. 相似文献
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Inside Back Cover: Stepwise Assembly of MII7 Clusters Revealed by Mass Spectrometry,EXAFS, and Crystallography (Chem. Eur. J. 51/2016) 下载免费PDF全文
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Niklas Rinn Dr. Jens P. Eußner Willy Kaschuba Dr. Xiulan Xie Prof. Dr. Stefanie Dehnen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(9):3094-3104
Reactions of R1SnCl3 (R1=CMe2CH2C(O)Me) with (SiMe3)2Se yield a series of organo‐functionalized tin selenide clusters, [(SnR1)2SeCl4] ( 1 ), [(SnR1)2Se2Cl2] ( 2 ), [(SnR1)3Se4Cl] ( 3 ), and [(SnR1)4Se6] ( 4 ), depending on the solvent and ratio of the reactants used. NMR experiments clearly suggest a stepwise formation of 1 through 4 by subsequent condensation steps with the concomitant release of Me3SiCl. Furthermore, addition of hydrazines to the keto‐functionalized clusters leads to the formation of hydrazone derivatives, [(Sn2(μ‐R3)(μ‐Se)Cl4] ( 5 , R3=[CMe2CH2CMe(NH)]2), [(SnR2)3Se4Cl] ( 6 , R2=CMe2CH2C(NNH2)Me), [(SnR4)3Se4][SnCl3] ( 7 , R4=CMe2CH2C(NNHPh)Me), [(SnR2)4Se6] ( 8 ), and [(SnR4)4Se6] ( 9 ). Upon treatment of 4 with [Cu(PPh3)3Cl] and excess (SiMe3)2Se, the cluster fragments to form [(R1Sn)2Se2(CuPPh3)2Se2] ( 10 ), the first discrete Sn/Se/Cu cluster compound reported in the literature. The derivatization reactions indicate fundamental differences between organotin sulfide and organotin selenide chemistry. 相似文献
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Ya-Shan Huang Yuan Xue Prof. Alvaro Muñoz-Castro Prof. Dr. Ivan A. Popov Prof. Dr. Zhong-Ming Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(62):e202202192
During the past two decades, single-atom-centered medium-sized germanium clusters [M@Gen] (M=transition metals, n>12) have been extensively explored, both from theoretical perspectives and experimental gas-phase syntheses. However, the actual structural arrangements of the Ge13 and Ge14 endohedral cages are still ambiguous and have long remained an unresolved problem for experimental implementation. In this work, we successfully synthesize 13-/14-vertex Ge clusters [Nb@Ge13]3− ( 1 ) and [Nb@Ge14]3− ( 2 ), which are structurally characterized and exhibit unprecedented topologies, neither classical deltahedra nor 3-connected polyhedral structures. Theoretical analysis indicates that the major stabilization of the Ge backbones arises due to the substantial interaction of Ge 4p-AOs with the endohedral Nb 4d-AOs through three/four-center two-electron bonds with an enhanced electron density accumulated over the shortest Nb−Ge13 contact in 1 . Low occupancies of the direct two-center two-electron (2c–2e) Nb−Ge and Ge−Ge σ bonds point to a considerable degree of electron delocalization over the Ge cages revealing their electron deficiency. 相似文献
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We study the origin of TB (tuberculosis) epidemic and complex distributions of various populations of TB infection within the stochastic framework. The stochastic nature of this disease infection could be linked to the stochastic behaviour at genome level which is exhibited in SNP (single nucleotide polymorphism) distributions of experimentally identified hotspot driver genes. Our results show the emergence of random clusters, and well-defined discrete domains of the respective species populations in the model driven by demographic stochasticity and intrinsic complex species interaction. The multifractal analysis of the time series of the species populations indicate that TB epidemic could be mainly caused by contact communication and is directional. We propose that any TB epidemic may have high chance of approximately periodic recurrence and can be controlled by optimizing some of the parameters involved in the system modelling. 相似文献
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Dr. Sanil E. Sivan Minhui Lee Su-Kyung Lee Dr. Ji Woong Yoon Dr. Kiwoong Kim Dr. Do-Young Hong Kyung-Ho Cho Dr. U-Hwang Lee Prof. Jong-San Chang Dr. Jaehoon Jung Prof. Young Kyu Hwang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12889-12894
Oxo-bridged trimeric chromium acetate clusters [Cr3O(OOCCH3)6(H2O)3]NO3 have been encapsulated for the first time in the mesoporous cages of the chromium terephthalate MIL-101(Cr). The isolated clusters in MIL-101(Cr) have increased affinity towards propylene compared to propane, due to generation of a new kind of pocket-based propylene-binding site, as supported by DFT calculations. 相似文献
9.
A series of new heteromultinuclear FeI/RuII clusters are described. The complexes (η6-arene)RuFe2S2(CO)6 (arene = p-cymene 1 , C6Me6 2 ) and Fe2[μ-S (Cp*Ru)(CO)2]2(CO)6 (Cp* = η5-C5Me5) ( 3 ) were prepared by the reduction reactions of (μ-S)2Fe2(CO)6 with 2 equiv of LiHBEt3, followed by treatment (μ-SLi)2Fe2(CO)6 with ruthenium-arene complexes Ru2(μ-Cl)2Cl2(η6-arene)2 or Cp*Ru (CO)2Cl in 22–33% yields. Further reactions of 1 and 2 with 1 equiv of triphenylphosphine in the presence of the decarbonylating agent Me3NO·2H2O, afforded the corresponding monophosphine-substituted FeI/RuII complexes (η6-arene)RuFe2S2(CO)5(Ph3P) (arene = p-cymene 4 , C6Me6 5 ) in 75% and 78% yields. While treatment of parent complex 1 or 2 with 1 equiv of diphosphine Ph2PCH2PPh2 (dppm) in xylene at reflux temperature resulted in the formation of the diphosphine-bridged RuFe2S2(CO)9 derivate RuFe2S2(CO)7(dppm) ( 6 ). The possible pathway for the formation was proposed. Two isomers of novel macrocyclic complexes involve the (η6-arene) Ru-bridged quadruple-butterfly Fe/S clusters [{μ-S (CH2)3S-μ}{(μ-CS2)Fe2(CO)6}2]2[(η6-arene)Ru]2 (arene = p-cymene 7a and 7b , C6Me6 8a and 8b ) were isolated by reactions of two μ-CS2-containing dianion [{μ-S (CH2)3S-μ}{(μ-S=CS)Fe2(CO)6}2]2− with [Ru2(μ-Cl)2Cl2(η6-arene)2], in which the propylene groups are attached to two S atoms by ee and ea types of bonds respectively. All the new complexes 1 – 8 have been characterized by elemental analysis, spectroscopy, and particularly for 1 – 6 , 7b and 8a by X-ray crystallography. In addition, the electrochemical properties of representative complexes 1 – 4 and 6 have been investigated. 相似文献
10.
Dimethyl furan-2, 5-dicarboxylate (DMFDCA) is a valuable biomass-derived chemical that is an ideal alternative to fossil-derived terephthalic acid as a monomer for polymers. The one-step oxidation of 5-hydroxymethylfurfural (HMF) to DMFDCA is of practical significance. It not only shortens the reaction pathway but also avoids the separation process of intermediates; thus, reducing cost. In this work, non-noble bimetallic catalysts supported on N-doped porous carbon (CoMn@NC) were synthesized via a one-step co-pyrolysis procedure using different pyrolysis temperatures and proportions of metal precursors and additives. We employed the prepared CoMn@NC catalysts in the aerobic oxidation of HMF under mild reaction conditions to obtain DMFDCA. High-yield DMFDCA was obtained by screening the prepared catalysts and optimizing the reaction conditions, including the strength and amount of the base, as well as the reaction temperature. The optimized yield of DMFDCA was 85% over the Co3Mn2@NC-800 catalyst after 12 h at 50 ℃ using ambient-pressure oxygen. The physicochemical properties of the catalysts were determined using a variety of characterization techniques, the factors affecting the performance of each catalyst were investigated, and the relationship between the physicochemical properties and performance of the prepared catalysts was elucidated. A porous structure with a high surface area had a positive effect on mass transfer efficiency. Cobalt nanoparticles (NPs) and atomically dispersed Mn were coordinated to N-doped carbon to form M―Nx (where M = Co or Mn). Based on the Mott-Schottky effect, there was significant electron transfer between each metal and the N-doped carbon, additionally, the metal NPs supplied electrons to the carbon atoms. The electron-deficient metal site in the pyridinic N-rich carbon was beneficial for the activation of HMF and oxygen. The activation of oxygen produced reactive oxygen species (such as superoxide radical anions) to ensure high selectivity to DMFDCA through dehydrogenative oxidation of the hemiacetal intermediate and hydroxymethyl group of 5-hydroxymethyl-2-methyl-furoate. The existence of disordered and defective carbons increased the number of active sites. Subsequently, we performed a series of control experiments. Based on our current experimental results and previous studies, we propose a simple mechanism for the aerobic oxidation of HMF to DMFDCA. The catalyst was stable, its performance decreased slightly after two cycles, and it was tolerant to SCN− ions and resistant against N or S poisoning. Furthermore, the use of this catalytic system can be expanded to various substituted aromatic alcohols, such as benzyl alcohols with different substituents, furfuryl alcohol, and heterocyclic alcohols. Simultaneously, the product type was further extended from methyl esters to ethyl esters with a high yield when the substrate reacted with ethanol. In conclusion, this catalytic system can be applied in the production of carboxylic esters for polymers.![]()
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