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1.
Antoine Barthélemy Dr. Harald Scherer Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(53):e202201369
The tetracationic, univalent cluster compounds [{M(dmpe)}4]4+ (M=Ga, In; dmpe=bis(dimethylphosphino)ethane) were synthesized as their pf salts ([pf]−=[Al(ORF)4]−; RF=C(CF3)3). The four-membered ring in [{M(dmpe)}4]4+ is slightly puckered for M=Ga and almost square planar for M=In. Yet, although structurally similar, only the gallium cluster is prevalent in solution, while the indium cluster forms temperature dependent equilibria that include even the monomeric cation [In(dmpe)]+. This system is the first report of one and the same ligand inducing formation of isoelectronic and isostructural gallium/indium cluster cations. The system allows to study systematically analogies and differences with thermodynamic considerations and bonding analyses, but also to outline perspectives for bond activation using cationic, subvalent group 13 clusters. 相似文献
2.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode 相似文献
3.
Edward G. Sheetz Zhao Zhang Alyssa Marogil Minwei Che Dr. Maren Pink Dr. Veronica Carta Prof. Dr. Krishnan Raghavachari Prof. Dr. Amar H. Flood 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201584
The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF3−). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF3−, by cyanostar macrocycles that are size-complementary to the inorganic BF4− progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K+ salts of R−BF3− anions. 相似文献
4.
5.
Yoshiyuki Mizuhata Shiori Fujimori 《Phosphorus, sulfur, and silicon and the related elements》2020,195(11):936-939
AbstractThe reaction of 2-t-Bu-germabenzenylpotassium with Me2(t-Bu)SiCl (TBDMSCl) resulted in the coupling among two TBDMS-substituted germabenzenes and the germabenzenylpotassium. The structure of the product was determined by X-ray crystallographic analysis. Its formation mechanism was proposed with the help of theoretical calculations. 相似文献
6.
Dr. Pu Bai Dr. Zhuoya Dong Dr. Shuang Wang Dr. Xiangyu Wang Dr. Yue Li Dr. Yunzheng Wang Prof. Dr. Yanhang Ma Prof. Dr. Wenfu Yan Prof. Dr. Xiaodong Zou Prof. Dr. Jihong Yu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19707-19712
Cationic framework materials, especially pure inorganic cationic frameworks that can efficiently and selectively capture harmful heavy metal oxyanions from aqueous solution are highly desired yet scarcely reported. Herein, we report the discovery of a 2D cationic aluminum oxyhydroxide, JU-111, which sets a new benchmark for heavy metal oxyanion sorbents, especially for CrVI. Its structure was solved based on 3D electron diffraction tomography data. JU-111 shows fast sorption kinetics (ca. 20 min), high capture capacity (105.4 mg g−1), and broad working pH range (3–10) toward CrVI oxyanions. Unlike layered double hydroxides (LDHs), which are poorly selective in the presence of CO32−, JU-111 retains excellent selectivity for CrVI even under a large excess of CO32−. These superior features coupled with the ultra-low cost and environmentally benign nature make JU-111 a promising candidate for toxic metal oxyanion remediation as well as other potential applications. 相似文献
7.
Dr. Yanmei Shi Wei Du Dr. Wei Zhou Dr. Changhong Wang Shanshan Lu Dr. Siyu Lu Prof. Bin Zhang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(50):22656-22660
Transition metal chalcogenides (TMCs) are efficient oxygen evolution reaction (OER) pre-electrocatalysts, and will in situ transform into metal (oxy)hydroxides under OER condition. However, the role of chalcogen is not fully elucidated after oxidation and severe leaching. Here we present the vital promotion of surface-adsorbed chalcogenates on the OER activity. Taking NiSe2 as an example, in situ Raman spectroscopy revealed the oxidation of Se-Se to selenites (SeO32−) then to selenates (SeO42−). Combining the severe Se leaching and the strong signal of selenates, it is assumed that the selenates are rich on the surface and play significant roles. As expected, adding selenites to the electrolyte of Ni(OH)2 dramatically enhance its OER activity. And sulfates also exhibit the similar effect, suggesting the promotion of surface-adsorbed chalcogenates on OER is universal. Our findings offer unique insight into the transformation mechanism of materials during electrolysis. 相似文献
8.
Marcel Aebli Bogdan M. Benin Kyle M. McCall Viktoriia Morad Debora Thöny Hansjörg Grützmacher Maksym V. Kovalenko 《Helvetica chimica acta》2020,103(7):e2000080
Inorganic lead halide perovskites have gained immense scientific interest for optoelectronic applications. In this work, we present a one-dimensional polymorph of cesium lead bromide (δ-CsPbBr3) synthesized through a simple anion-exchange reaction, wherein distorted edge-sharing PbBr6 octahedra form 1D chains isolated by Cs ions. δ-CsPbBr3 was characterized by Raman spectroscopy, X-ray diffraction, 207Pb and 133Cs solid-state NMR, and by optical emission and absorption spectroscopies. This non-perovskite material irreversibly transforms into the well-known three-dimensional perovskite phase (γ-CsPbBr3) upon heating to above 151 °C. The indirect bandgap was determined by absorption measurements and calculation to be 2.9 eV. δ-CsPbBr3 exhibits broadband yellow photoluminescence with a quantum yield of 3.2 %±0.2 % at room temperature and 95 %±5 % at 77 K, and this emission is attributed to the recombination of self-trapped excitons. This study emphasizes that the metastable δ-CsPbBr3 may be a persistent, concomitant phase in Cs−Pb-Br-containing materials systems, such as those used in solar cells and LEDs, and it showcases the characterization tools used for its detection. 相似文献
9.
新反应、新试剂的发展是有机合成化学的重要研究内容,基于前期在α-氨基丙二腈合成方法学方面的工作基础,我们发展了一例铜催化的α-氨基丙二腈的脱氰氧代反应.通过将甲酰胺转化为α-氨基丙二腈后,借助其亲核属性来合成α-氨基丙二腈底物,而后将底物重新转化为酰胺,从而实现形式上的氨基甲酰负离子的亲核加成(取代)反应.该工作首次完成了形式上的甲酰胺碳原子的极性反转,实现了将α-氨基丙二腈作为氨基甲酰负离子替代物的反应新模式,为叔酰胺化合物的合成提供了新的思路和方法,且具有反应条件简单,底物适用性广及适合克级规模制备等特点. 相似文献
10.
Chinomso Nwosu Tara P. Pandey Andrew M. Herring Soenke Seifert E. Bryan Coughlin 《Journal of polymer science. Part A, Polymer chemistry》2020,58(24):3446-3455
Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2–8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3–6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60°C. Conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90°C. 相似文献