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11.
12.
Specimens of iron-doped indium oxide (In1-xFex)2O3 with x?=?0.015, 0.03, 0.045 and 0.06, amalgamated through a traditional solid-state reaction method followed by H2/air sintering, were characterised using an X-ray diffractometer (XRD), a vibrating sample magnetometer (VSM), and a scanning electron microscope (SEM) to investigate their structural, magnetic and morphological properties respectively. According to XRD plots, all the specimens exhibit cubic bixbyite structures along with ancillary phases. Magnetic assessment showed that In2O3 has a negative susceptibility, exhibiting diamagnetic behaviour at room temperature. The doping of Fe ions induces ferromagnetic (FM) ordering, which is enhanced with increasing doping content. The strength of the magnetisation increases when the specimens are exposed to H2 but is reduced on further air sintering. A bound magnetic polaron (BMP) model is successfully fitted to the observed FM data involving localised carriers and magnetic cations. A multivariate assessment viz. a hierarchical cluster analysis (HCA) was used to corroborate and strengthen the experimental determined magnetic properties. A homogeneous particle distribution was observed in all SEM micrographs and is validated through MATLAB-based simulation by applying a watershed segmentation algorithm. Surface plots also confirm the change in magnetic properties with increase in doping concentration. 相似文献
13.
ABSTRACTModified coupled-cluster (CC) methods such as linearized coupled-cluster doubles (LinCCD), approximate coupled pair (ACP D14), 2CC (from nCC family), parameterized CCSD (pCCSD) and distinguishable cluster (DCSD) can have their advantages over general CC methods. Though these methods include connected clusters of single and double excitations at most, distinguishable cluster, parameterized CC and approximate coupled pair methods, in particular, have been shown to produce quantitatively correct results in benchmark studies. To put these methods on a stronger foothold, it is essential to understand the rationale for their success: mimicking the effect of connected triple excitations. We exploit the relation between CC and many body perturbation theory (MBPT) in general, and between CCSD and MBPT(4)/MP4 in particular, to take a step towards bringing clarity to this persisting conundrum. Our aim here is to look for numerical signs of ‘addition by subtraction’ or ‘inclusion by deletion’ effect that is likely behind the success of these modified CCD or CCSD methods. We achieve this by revisiting well-studied examples of single and multiple bond dissociation and comparing the performance of these modified CCSD methods with higher-level CC methods. Though our results are qualitative in nature, we hope this would lead to more rigorous analysis in future studies. 相似文献
14.
Mitsuki Yamashita Yuna Kawasumi Yuki Tachibana Dr. Shinnosuke Horiuchi Dr. Koji Yamamoto Prof. Tetsuro Murahashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(5):1212-1216
Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd4]4+ chain. 相似文献
15.
Li‐Na Wang Zhen‐Xun Zhou Dr. Xiao‐Na Li Dr. Tong‐Mei Ma Prof. Sheng‐Gui He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6957-6961
In addition to generation of a methyl radical, formation of a formaldehyde molecule was observed in the thermal reaction of methane with AuNbO3+ heteronuclear oxide cluster cations. The clusters were prepared by laser ablation and mass‐selected to react with CH4 in an ion‐trap reactor under thermal collision conditions. The reaction was studied by mass spectrometry and DFT calculations. The latter indicated that the gold atom promotes formaldehyde formation through transformation of an Au?O bond into an Au?Nb bond during the reaction. 相似文献
16.
Reactions with a Metalloid Tin Cluster {Sn10[Si(SiMe3)3]4}2−: Ligand Elimination versus Coordination Chemistry 下载免费PDF全文
Dr. Claudio Schrenk Birgit Gerke Prof. Dr. Rainer Pöttgen Dr. Andre Clayborne Prof. Dr. Andreas Schnepf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8222-8228
Chemistry that uses metalloid tin clusters as a starting material is of fundamental interest towards understanding the reactivity of such compounds. Since we identified {Sn10[Si(SiMe3)3]4}2? 7 as an ideal candidate for such reactions, we present a further step in the understanding of metalloid tin cluster chemistry. In contrast to germanium chemistry, ligand elimination seems to be a major reaction channel, which leads to the more open metalloid cluster {Sn10[Si(SiMe3)3]3}? 9 , in which the Sn core is only shielded by three Si(SiMe3)3 ligands. Compound 9 is obtained through different routes and is crystallised together with two different countercations. Besides the structural characterisation of this novel metalloid tin cluster, the electronic structure is analysed by 119Sn Mössbauer spectroscopy. Additionally, possible reaction pathways are discussed. The presented first step into the chemistry of metalloid tin clusters thus indicates that, with respect to metalloid germanium clusters, more reaction channels are accessible, thereby leading to a more complex reaction system. 相似文献
17.
Back Cover: Ligand Symmetry Modulation for Designing a Mesoporous Metal–Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization (Chem. Eur. J. 27/2015) 下载免费PDF全文
18.
Yuwei Wang Jia-Jun Yan Shengnan Hu Prof. David James Young Prof. Hong-Xi Li Prof. Zhi-Gang Ren 《化学:亚洲杂志》2021,16(18):2681-2686
A photoluminescent bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(MeOH)2(H2O)](ClO4)4 ( 1 , bdppthi=N,N’-bis(diphenylphosphanylmethyl)-tetrahydroimidazole} was synthesized from the PNNP type ligand bdppthi generated in-situ. Upon excitation at 365 nm, 1 exhibited strong phosphorescent emission at 630 nm, which was selectively quenched by NH3 in air or water. The sensing of NH3 was rapid and recoverable, with detection limits of 53 ppm (v/v) in N2 and 21 μmol/L (0.36 ppm, w/w) for NH3 ⋅ H2O in water. Cluster 1 could potentially serve as a bifunctional chemical sensor for the efficient detection of ammonia in waste-gas and waste-water. 相似文献
19.
Six new carbonate-bridged Zn2Ln2 cluster complexes derived from salen-type Schiff base ligands [H2La = N, N′-bis(3-methoxysalicylidene)-1,3-diaminopropane and H2Lb = N, N′-bis(3-methoxysalicylidene)- 1,2-diaminoethane] have been synthesized. The bis-imine chain in Schiff base ligands have an obvious influence on the cluster complexes' structures, magnetic and luminescence properties. The carbonate bridging ligand exactly comes from autoimmobilization of carbon dioxide, which may mediate ferromagnetic coupling between Ln3+ ions, favoring magnetocaloric effects and single molecule magnet (SMM) properties. Complexes Zn2Dy2(μ3-CO3)2(La)2(NO3)2(MeOH)2 ( 1 ) and [Zn2Dy2(μ3-CO3)2(Lb)2(NO3)2]·2MeOH ( 2) show field-induced SMM properties; complexes Zn2Tb2(μ3-CO3)2(La)2(NO3)2(MeOH)2 ( 3 ) and [Zn2Tb2(μ3-CO3)2(Lb)2(NO3)2]·2MeOH ( 4 ) display both luminescence and field-induced SMM behaviors; while complexes [Zn2Gd2(μ3-CO3)2(La)2(NO3)2]·2MeOH ( 5 ) and [Zn2Gd2(μ3-CO3)2(Lb)2(NO3)2]·2MeOH ( 6 ) exhibit medium magnetic entropy changes, which are candidates for cryogenic molecular magnetic refrigerants. 相似文献
20.
Yu-Yi Zhang De-Shan Zhang Tian Li Dr. Mohamedally Kurmoo Prof. Dr. Ming-Hua Zeng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):721-728
Dehydration of (S,S)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethane-1,2-diol (H4L) to (Z)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethenol) (H3L′) was found to be metal-assisted, occurs under solvothermal conditions (H2O/CH3OH), and leads to [MnII4(H3L)4Cl2]Cl2 ⋅ 5 H2O ⋅ 5 CH3OH ( Mn4L4 ) and [MnII4(H2L′)6(μ3-OH)]Cl ⋅ 4 CH3OH ⋅ H2O ( Mn4L′6 ), respectively. Their structures were determined by single-crystal XRD. Extensive ESI-MS studies on solutions and solids of the reaction led to the proposal consisting of an initial stepwise assembly of Mn4L4 from the reactants via [MnL] and [Mn2L2] below 80 °C, and then disassembly to [MnL] and [MnL2] followed by ligand modification before reassembly to Mn4L′6 via [MnL′], [MnL′2], and [Mn2L′3] with increasing solvothermal temperature up to 140 °C. Identification of intermediates [Mn4LxL′6−x] (x=5, 4, 3, 2, 1) in the process further suggested an assembly/disassembly/in situ reaction/reassembly transformation mechanism. These results not only reveal that multiple phase transformations are possible even though they were not realized in the crystalline state, but also help to better understand the complex transformation process between coordination clusters during “black-box” reactions. 相似文献