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1.
Huixin Fan Chensheng Lin Kaichuang Chen Guang Peng Bingxuan Li Ge Zhang Xifa Long Ning Ye 《Angewandte Chemie (International ed. in English)》2020,59(13):5268-5272
An ammonium‐containing metal iodate fluoride compound, (NH4)Bi2(IO3)2F5, featuring a two‐dimensional double‐layered framework constructed by [BiO2F5]6? and [BiO4F4]9? polyhedra, as well as [IO3]? groups, was successfully synthesized. The well‐ordered alignment of these SHG‐active units leads to an extraordinary strong SHG response of 9.2 times that of KDP. Moreover, this compound possesses a large birefringence (Δn=0.0690 at 589.3 nm), a wide energy band gap (Eg=3.88 eV), and a high laser damage threshold (LDT; 40.2×AgGaS2). In particular, thermochromic behavior was observed for the first time in this type of compound. Such multifunctional crystals will expand the application of nonlinear optical materials. 相似文献
2.
Fei‐Fei Mao Dr. Chun‐Li Hu Dr. Xiang Xu Dong Yan Dr. Bing‐Ping Yang Prof. Jiang‐Gao Mao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(8):2183-2187
The first metal iodate fluoride, Bi(IO3)F2, with a strong second harmonic generation (SHG) effect has been prepared. Bi(IO3)F2 crystallizes in the polar space group C2 and features a three‐dimensional [BiF2]+ cationic framework with IO3 groups capping the inner walls of the one‐dimensional tunnels. This [BiF2]+ cationic framework acts as a template for the assembly of the polar IO3 units in a favorable superposed fashion, which leads to the polar structure of the material. Bi(IO3)F2 displays a rather wide transmittance window (0.3–11 μm) and exhibits a very strong SHG response that is about 11.5 times larger than that of KH2PO4 (KDP) under 1064 nm laser radiation and the same as that of KTiOPO4 (KTP) under 2.05 μm laser radiation. Preliminary investigations indicate that Bi(IO3)F2 is a promising nonlinear optical material in the visible and mid‐IR region. 相似文献
3.
ASb2(SO4)2(PO4) (A = H3O+, K,Rb): Layered Structure Containing Ordered Sulfate and Phosphate Anions 下载免费PDF全文
Three compounds ASb2(SO4)2(PO4) (A = H3O+, K, Rb) were obtained from the reactions of Sb2O3, A2CO3 (A = Li, Rb) or K2SO4 and NH4H2PO4 in H2SO4 (98 %) at 220–250 °C. Their structures were determined by single‐crystal X‐ray diffraction. All compounds crystallize in the triclinic space group P$\bar{1}$ (no.2) and are isostructural. The crystal structures consist of two‐dimensional 2∞[Sb2(SO4)2(PO4)]– anionic layers and alkali cations, which are located between anionic layers. The anionic layers are composed of [SbO4] ψ‐trigonal bipyramids, [SbO5] ψ octahedra, [SO4] tetrahedra, and [PO4] tetrahedra. All compounds are characterized by solid state UV/Vis/NIR diffuse reflectance spectra, FT‐IR spectroscopy, and Raman spectroscopy. 相似文献
4.
Ruiqi Wang Fei Liang Fakun Wang Yangwu Guo Xian Zhang Yi Xiao Kejun Bu Zheshuai Lin Jiyong Yao Tianyou Zhai Fuqiang Huang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(24):8162-8165
A new nonlinear optical (NLO) oxysulfide, Sr6Cd2Sb6O7S10, which contains the functional groups [SbOxS5?x]7? (x=0, 1) with a 5s2 electron configuration, is synthesized by a solid‐state reaction. This compound displays a phase‐matchable second harmonic generation (SHG) response four times stronger than AgGaS2 (AGS) under laser irradiation at 2.09 μm. Single‐crystal‐based optical measurements reveal a SHG intensity that can be tuned by temperature and novel photoluminescence properties. Theoretical analyses demonstrate that tetragonal [SbOS4]7? and [SbS5]7? pyramids make the predominant contribution to the enhanced SHG effect. Among those, the [SbOS4]7? units with mixed anions make a larger contribution. This work proposes that oxysulfide groups with an ns2 electron configuration can serve as new functional building units in NLO materials and opens a new avenue for the design of other optoelectronic materials. 相似文献
5.
Vratislav Langer Barbara M. Casari 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(4):i25-i27
A novel structure type of an acidic rare‐earth sulfate, hexapotassium cerium dihydrogensulfate tetrasulfate monohydrate, is reported. The crystal is twinned, mimicking tetragonal symmetry. The CeIV atom is nine‐coordinate, connecting to one corner‐sharing and four edge‐sharing sulfate groups. One of the potassium ions is disordered over two general positions. The compound is unique as it contains rare‐earth monomers, [Ce(HSO4)(SO4)4]5−. The structure is composed of these monomers, water molecules, discrete hydrogensulfate ions and potassium ions held together by ionic interactions. There are two types of alternating layers in the structure, with compositions [K4Ce(HSO4)(SO4)4]− and [K2(HSO4)(H2O)]+. 相似文献
6.
Jin Chen Chun‐Li Hu Xiao‐Han Zhang Bing‐Xuan Li Bing‐Ping Yang Jiang‐Gao Mao 《Angewandte Chemie (International ed. in English)》2020,59(13):5381-5384
The first alkali‐metal vanadium iodate fluoride, CsVO2F(IO3), with a novel 3D anionic framework, has been rationally designed and hydrothermally synthesized. The 3D [VO2F(IO3)]? framework in CsVO2F(IO3) is built from 0D Λ‐shaped cis‐[VO3F(IO3)2]4? polyanions via corner‐sharing of oxo anions and bridging of the iodate groups. CsVO2F(IO3) displays both a strong second‐harmonic generation (SHG) 1.1 times as strong as KTiOPO4 (KTP) under 2.05 μm laser radiation and high laser‐induced damage threshold (LIDT) of 107.9 MW cm?2. This work provides a new route to design SHG crystals with stable 3D anionic structures from low‐dimensional structural building units. 相似文献
7.
Dr. Huixin Fan Prof. Chensheng Lin Kaichuang Chen Dr. Guang Peng Dr. Bingxuan Li Prof. Ge Zhang Prof. Xifa Long Prof. Ning Ye 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(13):5306-5310
An ammonium-containing metal iodate fluoride compound, (NH4)Bi2(IO3)2F5, featuring a two-dimensional double-layered framework constructed by [BiO2F5]6− and [BiO4F4]9− polyhedra, as well as [IO3]− groups, was successfully synthesized. The well-ordered alignment of these SHG-active units leads to an extraordinary strong SHG response of 9.2 times that of KDP. Moreover, this compound possesses a large birefringence (Δn=0.0690 at 589.3 nm), a wide energy band gap (Eg=3.88 eV), and a high laser damage threshold (LDT; 40.2×AgGaS2). In particular, thermochromic behavior was observed for the first time in this type of compound. Such multifunctional crystals will expand the application of nonlinear optical materials. 相似文献
8.
Mathias S. Wickleder 《无机化学与普通化学杂志》1999,625(2):302-308
LiLa2F3(SO4)2 and LiEr2F3(SO4)2: Fluoride‐Sulfates of the Rare‐Earth Elements with Lithium The reaction of LiF with the anhydrous sulfates M2(SO4)3 (M = La, Er) in sealed gold ampoules yields single crystals of the pseudo quaternary compounds LiLa2F3(SO4)2 and LiEr2F3(SO4)2. According to X‐ray single crystal investigations, LiLa2F3(SO4)2 crystallizes with the monoclinic (I2/a, Z = 4, a = 828.3(2), b = 694.7(1), c = 1420.9(3) pm, β = 95.30(2)°, Rall = 0.0214) and LiEr2F3(SO4)2 with the orthorhombic crystal system (Pbcn, a = 1479.1(2), b = 633.6(1), c = 813.7(1) pm, Rall = 0.0229). A common feature of both structures is a dimeric unit of metal atoms connected via three fluoride ions. This leads to relatively short metal‐metal distances (La3+–La3+: 389 pm, Er3+–Er3+: 355 pm). In LiLa2F3(SO4)2, Li+ is surrounded by four oxygen atoms of four sulfate groups and one fluoride ion in form of a trigonal bipyramid, in LiEr2F3(SO4)2 two further fluoride ligands are attached. 相似文献
9.
Y. Xia J. I. Friese D. A. Moore L. Rao 《Journal of Radioanalytical and Nuclear Chemistry》2006,268(3):445-451
Summary A solvent extraction method was used to determine the stability constants of Np(V) complexes with fluoride and sulfate in
1.0M NaClO4 from 25 to 60 °C. The distribution ratio of Np(V) between the organic and aqueous phases was found to decrease as the concentrations
of fluoride and sulfate were increased. Stability constants of the 1 : 1 Np(V)-fluoride complexes and the 1 : 1 Np(V)-sulfate
and 1 : 2 Np(V)-sulfate complexes, dominant in the aqueous phase under the experimental conditions, were calculated from the
effect of [F-] and [SO42-] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different
temperatures by using the Van't Hoff equation. 相似文献
10.
Jun‐Liang Liu Kasper S. Pedersen Samuel M. Greer Itziar Oyarzabal Abhishake Mondal Stephen Hill Fabrice Wilhelm Andrei Rogalev Alain Tressaud Etienne Durand Jeffrey R. Long Rodolphe Clrac 《Angewandte Chemie (International ed. in English)》2020,59(26):10306-10310
Silicon‐mediated fluoride abstraction is demonstrated as a means of generating the first fluorido‐cyanido transition metal complexes. This new synthetic approach is exemplified by the synthesis and characterization of the heteroleptic complexes, trans‐[MIVF4(CN)2]2? (M=Re, Os), obtained from their homoleptic [MIVF6]2? parents. As shown by combined high‐field electron paramagnetic resonance spectroscopy and magnetization measurements, the partial substitution of fluoride by cyanide ligands leads to a marked increase in the magnetic anisotropy of trans‐[ReF4(CN)2]2? as compared to [ReF6]2?, reflecting the severe departure from an ideal octahedral (Oh point group) ligand field. This methodology paves the way toward the realization of new heteroleptic transition metal complexes that may be used as highly anisotropic building‐blocks for the design of high‐performance molecule‐based magnetic materials. 相似文献
11.
Masato Hashimoto Michiru Kubata Atsushi Yagasaki 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(12):1411-1412
The title compound, triammonium cis‐diaqua‐cis‐dioxo‐trans‐disulfatovanadate 1.5‐hydrate, was obtained by oxidizing VIV to VV in a 2 M sulfuric acid solution of vanadyl sulfate and adding ammonium sulfate. Here, the V atom is sandwiched by two sulfate groups by corner‐sharing to form a discrete [VO2(SO4)2(OH2)2]3? anion. The water molecules occupy cis positions in the equatorial plane of the vanadium octahedron. 相似文献
12.
Dr. Thies Olaf Petersen Dustin Simone Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15847-15855
Attempts to prepare previously unknown simple and very Lewis acidic [RZn]+[Al(ORF)4]? salts from ZnR2, AlR3, and HO?RF delivered the ion‐like RZn(Al(ORF)4) (R=Me, Et; RF=C(CF3)3) with a coordinated counterion, but never the ionic compound. Increasing the steric bulk in RZn+ to R=CH2CMe3, CH2SiMe3, or Cp*, thus attempting to induce ionization, failed and led only to reaction mixtures including anion decomposition. However, ionization of the ion‐like EtZn(Al(ORF)4) compound with arenes yielded the [EtZn(arene)2]+[Al(ORF)4]? salts with arene=toluene, mesitylene, or o‐difluorobenzene (o‐DFB)/toluene. In contrast to the ion‐like EtZn(η3‐C6H6)(CHB11Cl11), which co‐crystallizes with one benzene molecule, the less coordinating nature of the [Al(ORF)4]? anion allowed the ionization and preparation of the purely organometallic [EtZn(arene)2]+ cation. These stable materials have further applications as, for example, initiators of isobutene polymerization. DFT calculations to compare the Lewis acidities of the zinc cations to those of a large number of organometallic cations were performed on the basis of fluoride ion affinity. The complexation energetics of EtZn+ with arenes and THF was assessed and related to the experiments. 相似文献
13.
Unexpected Self‐Sorting Self‐Assembly Formation of a [4:4] Sulfate:Ligand Cage from a Preorganized Tripodal Urea Ligand 下载免费PDF全文
Dr. Komala Pandurangan Dr. Jonathan A. Kitchen Dr. Salvador Blasco Dr. Elaine M. Boyle Bella Fitzpatrick Dr. Martin Feeney Prof. Paul E. Kruger Prof. Thorfinnur Gunnlaugsson 《Angewandte Chemie (International ed. in English)》2015,54(15):4566-4570
The design and synthesis of tripodal ligands 1 – 3 based upon the N‐methyl‐1,3,5‐benzenetricarboxamide platform appended with three aryl urea arms is reported. This ligand platform gives rise to highly preorganized structures and is ideally suited for binding SO42? and H2PO4? ions through multiple hydrogen‐bonding interactions. The solid‐state crystal structures of 1 – 3 with SO42? show the encapsulation of a single anion within a cage structure, whereas the crystal structure of 1 with H2PO4? showed that two anions are encapsulated. We further demonstrate that ligand 4 , based on the same platform but consisting of two bis‐urea moieties and a single ammonium moiety, also recognizes SO42? to form a self‐assembled capsule with [4:4] SO42?: 4 stoichiometry in which the anions are clustered within a cavity formed by the four ligands. This is the first example of a self‐sorting self‐assembled capsule where four tetrahedrally arranged SO42? ions are embedded within a hydrophobic cavity. 相似文献
14.
During the reaction of Na2[WO4] with YF3 purposed to yield fluoride‐derivatized yttrium oxotungstates(VI), colourless platelet‐shaped single crystals of Na3F[WO4] emerged as main product. The title compound crystallizes orthorhombically in the space group Pnma (a = 559.59(5), b = 751.02(7), c = 1285.98(9) pm) with four formula units per unit cell. Besides isolated ortho‐oxotungstate units [WO4]2? (d(W–O) = 176–178 pm) the crystal structure contains two crystallographically independent Na+ cations which are both octahedrally coordinated by four oxygen atoms and two fluoride anions. The F? anions are surrounded by six sodium cations (d(F–Na) = 224–242 pm) also in an octahedral fashion. These octahedra built up chains along [100] by sharing trans‐oriented faces according to , which are stacked according to a hexagonal closest rod‐packing. The cationic strands are surrounded, interconnected and charge‐balanced by isolated [WO4]2? tetrahedra with almost ideal shape and every O2? ligand is terminally coordinated by three Na+ cations. 相似文献
15.
Aroyleneimidazophenazine: A Sensitive Probe for Detecting CN− Anion and its Solvatochromism Effect 下载免费PDF全文
J. Zhao J. Li G. Li J. Gao S. L. A. Kjelleberg S. C. J. Loo Q. Zhang 《Journal of heterocyclic chemistry》2015,52(6):1699-1704
A novel electron‐deficient heteroacene 15H‐pyrazino[2″,3″:3′,4′]pyrrolo[1′,2′:1,2]imidazo[4,5‐b]phenazin‐15‐one ( 1 ) has been successfully synthesized and characterized. Compound 1 can selectively recognize CN? and F? over other 10 anions including BF4?, PF6?, Cl?, SO42?, NO3?, I?, H2PO4?, ClO4?, Ac?, and Br? in CHCl3/DMF mixed solvents with dual responses, including absorption signals and fluorescent “turn‐off” effects. CN? and F? can be distinguished by the completely quenched fluorescence (for CN?) and partially reduced fluorescence (for F?). Especially, compound 1 exhibits higher sensitivity to CN? than F? with the response concentration as low as 5.0 × 10?6 mol/L. Moreover, compound 1 shows very interesting solvatochromism effect, and the CHCl3 solution of compound 1 is sensitive to triethylamine, and its emission could change from green to red upon the addition of triethylamine, which is attributed to the n–π intermolecular charge‐transfer interaction. 相似文献
16.
Niloofar Tavakoli‐Hoseini Raheleh Moloudi Abolghasem Davoodnia Mohammad Shaker 《中国化学》2011,29(11):2421-2426
A convenient and efficient method for the synthesis of pyrazolo[3,4‐d]pyrimidin‐4‐ones via heterocyclization reaction of 5‐amino‐1H‐pyrazole‐4‐carboxamides with triethyl orthoesters using two Br?nsted‐acidic ionic liquids, 3‐methyl‐1‐(4‐sulfonic acid)butylimidazolium hydrogen sulfate [MIM+(CH2)4SO3H][HSO4?] or N‐(4‐sulfonic acid)butyl triethylammonium hydrogen sulfate [Et3N+(CH2)4SO3H][HSO4?], as efficient homogeneous catalysts under solvent‐free conditions is described. 相似文献
17.
M. Sc. Benjamin Scheibe Clemens Pietzonka M. Sc. Otto Mustonen Prof. Dr. Maarit Karppinen Prof. Dr. Antti J. Karttunen Prof. Dr. Mihail Atanasov Prof. Dr. Frank Neese Dr. Matthias Conrad Prof. Dr. Florian Kraus 《Angewandte Chemie (International ed. in English)》2018,57(11):2914-2918
The D2h‐symmetric dinuclear complex anion [U2F12]2? of pastel green Sr[U2F12] shows a hitherto unknown structural feature: The coordination polyhedra around the U atoms are edge‐linked monocapped trigonal prisms, the UV atoms are therefore seven‐coordinated. This leads to a U–U distance of 3.8913(6) Å. A weak UV–UV interaction is observed for the dinuclear [U2F12]2? complex and described by the antiferromagnetic exchange Jexp of circa ?29.9 cm?1. The crystalline compound can be easily prepared from SrF2 and β‐UF5 in anhydrous hydrogen fluoride (aHF) at room temperature. It was studied by means of single crystal X‐ray diffraction, IR, Raman and UV/VIS spectroscopy, magnetic measurements, and by molecular as well as by solid‐state quantum chemical calculations. 相似文献
18.
Er4F2[Si2O7][SiO4]: The First Rare‐Earth Fluoride Silicate with Two Different Silicate Anions By the reaction of Er2O3 with ErF3 and SiO2 at 700 °C in sealed tantalum capsules using CsCl as flux (molar ratio 5 : 2 : 3 : 20), the compound Er4F2[Si2O7][SiO4] (triclinic, P 1; a = 648.51(5), b = 660.34(5), c = 1324.43(9) pm, α = 87.449(8), β = 85.793(8), γ = 60.816(7)°; Vm = 148.69(1) cm3/mol, Z = 2) is obtained as pale pink platelets or lath‐shaped single crystals. It consists of disilicate anions [Si2O7]6– in eclipsed conformation, ortho‐silicate anions [SiO4]4– and isolated [Er4F2]10+ units comprising two edge‐shared [Er3F] triangles. Er3+ is surrounded by 7 + 1 (Er1) or 7 (Er2–Er4) anionic neighbors, respectively, of which two are F– in the case of Er1 and Er4 but only one for Er2 and Er3. The other ligands recruit from oxygen atoms of the different oxosilicate groups. The crystal structure can be described as simple rowing up of the three building groups ([SiO4]4–, [Er4F2]10+, and [Si2O7]6–) along [001]. The necessity of a large excess of fluoride for a successful synthesis of Er4F2[Si2O7][SiO4] will be discussed. 相似文献
19.
Dichlorophosphate Complexes of the Nitrido Chlorides of Molybdenum and Tungsten Tetraphenylarsonium dichlorophosphate AsPh4[PO2Cl2], is prepared by the reaction of AsPh4Cl with P2O3Cl4. The vibrational spectrum is reported as well as the valence force constants of the [PO2Cl2]? ion. The f-values are clearly smaller than those of the isoelectronic SO2Cl2 molecule. The dichlorophosphate ion forms complexes with the nitride chlorides MNCl3 (M ? Mo, W) of the type [MNCl3(PO2Cl2)]22?, which are characterized by their i.r. spectra. 相似文献
20.
N. M. Laptash E. V. Kovaleva A. A. Mashkovskii A. Yu. Beloliptsev L. A. Zemnukhova 《Journal of Structural Chemistry》2007,48(5):848-854
Vibrational and 17O NMR spectroscopy in combination with quantum chemical calculations are used to investigate the hydrolysis of antimony(III) fluoride complexes. A hydrolytic decomposition of SbF3 and [SbF4]? is accompanied by oligomerization with the formation of edge-and corner-connected dimers ([Sb2O2F4]2?, [Sb2OF8]4?) and trimers ([Sb3O3F6]3?, [Sb3OF9]2?) with bridging oxygen atoms. The hydrolysis of [SbF4]? is also characterized by the presence in the solution of a discrete cation of [SbF5]2? which is least hydrolized. Only a partial isomorphic substitution of fluoride ion by hydroxide one is possible, which is reflected in the composition of K2Sb(OH)xF5?x (x = 0.3) crystals isolated from the fluoride aqueous solution. 相似文献