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1.
用DFT的B3LYP方法在6-31G(d)基组的水平上, 对闭式多面体簇合物(HAlNH)12及其内含式X@(HAlNH)12和外接式X(HAlNH)12 (X=F, Cl, Br, O2-, S2-, Se2-)复合物的结构进行了构型优化和能量计算, 并讨论了几何构型、自然键轨道(NBO)、振动频率、能量参数及NMR数据与结构的关系, 最后得到复合物结构的稳定性信息, 具有Th对称性的X@(HAlNH)12 (X=F, Cl, Br, S2-, Se2-)复合物和具有C3对称性的O2-@(HAlNH)12复合物为内含式的基态结构, 从能量角度分析, 内含式复合物比外接式复合物的结构稳定.  相似文献   

2.
张彩云  武海顺 《化学学报》2005,63(11):979-984
用DFT的B3LYP方法在6-31G(d)基组的水平上, 对闭式多面体簇合物(HAlNH)12及其内含式X@(HAlNH)12和外接式X(HAlNH)12 (X=F, Cl, Br, O2-, S2-, Se2-)复合物的结构进行了构型优化和能量计算, 并讨论了几何构型、自然键轨道(NBO)、振动频率、能量参数及NMR数据与结构的关系, 最后得到复合物结构的稳定性信息, 具有Th对称性的X@(HAlNH)12 (X=F, Cl, Br, S2-, Se2-)复合物和具有C3对称性的O2-@(HAlNH)12复合物为内含式的基态结构, 从能量角度分析, 内含式复合物比外接式复合物的结构稳定.  相似文献   

3.
The following ions [UO2(NO3)3], [UO2(ClO4)3], [UO2(CH3COO)3] were generated from respective salts (UO2(NO3)2, UO2(ClO4)3, UO2(CH3COO)2) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO4 ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an UVI compound, in which oxygen atoms bear unpaired electron and negative charge.  相似文献   

4.
It was determined by ESR spectroscopy that the UV irradiation of toluene solutions containing Hg[P(O)(OPri)2 and the complex (2-C60)Os(CO)(PPh3)2(CNBut) produces six stable regioisomeric adducts of phosphoryl radicals with complexes, which are not demetallated under UV irradiation and do not dimerize in the absence of UV irradiation. This is caused by the addition of the phosphoryl radicals to the carbon atoms of fullerene localized near the metal-containing moiety. The addition of the phosphoryl radicals to (2-C70)Os(CO)(PPh3)2(CNBut) gives rise to the formation of nine stable regioisomeric radical adducts. A comparison of the composition of regioisomers of the radical adducts of C70 with the phosphoryl radicals, which were formed directly from C70 and from the radical adducts of 2-C70)Os(CO)(PPh3)2(CNBut) by the demetallation of the latter, revealed an orienting effect of the osmium-containing moiety on the addition of the phosphoryl radicals to the fullerene complex.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1968–1972, September, 2004.  相似文献   

5.
6.
采用高温固相法在空气中合成了Ba1.97-yZn1-xMgxSi2O7:0.03Eu,yCe3+系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba1.97-yZn1-xMgxSi2O7:0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu2+离子的4f65d1-4f7跃迁,590~725 nm红光区窄带谱源于Eu3+5D0-7FJ (J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu3+在Ba1.97-yZn1-xMgxSi2O7基质中被还原成了Eu2+;当x=0.1时,荧光粉Ba1.97Zn0.9Mg0.1Si2O7:0.03Eu的绿色发光最强,表明Eu3+被还原成Eu2+离子的程度最大。当共掺入Ce3+离子后,形成Ba1.97-yZn0.9Mg0.1Si2O7:0.03Eu,yCe3+荧光粉体系,其发光随着Ce3+离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba1.96Zn0.9Mg0.1Si2O7:0.01Ce3+,0.03Eu的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba2Zn0.9Mg0.1Si2O7基质中的能量传递与发光机理。  相似文献   

7.
IR and single-crystal X-ray diffraction study are carried out for compound, C36H112Cl9Fe3N18O8P6(I). It crystallizes in the orthorhombic space group P212121 with a = 14.2992(3), b = 21.4351(4), c = 25.5407(5) ?, V = 7828.3(3) ?3, ρcalcd = 1.553 g/cm3, Z = 4. The FeCl fragment is coordinated with chlorine atom of two water molecules and three HMPA molecules to form a cation, with a distorted octahedral coordinate geometry. In the crystal I, the cation is linked with HMPA by the O-H…O hydrogen bond. The chiral crystal is formed through self-assembly even from achiral molecules.  相似文献   

8.

Abstract  

The complex [Fe(C6H4N2S2)3]2+(NO3)2 was prepared from the reaction of 4,4′-bithiazole with Fe(NO3)3·9H2O in methanol. It was characterized by IR, UV-Vis, luminescence, 1H NMR and 13C NMR spectroscopy, and X ray crystallography. The structure was solved in the orthorhombic space group P212121 with a = 12.1500(5), b = 12.8434(6), c = 16.2222(7) ?, V = 2531.43(19) ?3, Z = 4, and with wR 2  = 0.0897.  相似文献   

9.
Two novel ethylenediaminium salt of europium complexes with aminopolycarboxylic acid ligands, (EnH2)3[EuIII(Ttha)]2 · 11H2O (I) (En is ethylenediamine, H6Ttha is triethylenetetramine-N,N,N′,N″,N‴,N‴-hexaacetic acid) and (EnH2)[EuIII(Egta)(H2O)]2 · 6H2O (II) (H4Egta is ethyleneglycol-bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid) complexes were synthesized, and their crystal structures were determined by single-crystal X-ray diffraction techniques. Both of the two complexes adopt nine-coordinate structures with the pseudo-monocapped square antiprism and crystallize in the monoclinic crystal system with the P21/n space group. The crystal data for complex I are as follows: a = 17.8262(8), b = 19.3137(5), c = 20.6233(8) ?, β = 111.301(2)°, V = 6615.3(4) ?3, Z = 8, ρ c = 1.677 mg/m3, μ = 1.981 mm−1, F(000) = 3432, R = 0.0308, and wR = 0.0737 for 43622 observed reflections with I ≥ 2σ(I). The crystal data for complex II are as follows: a = 12.952(3), b = 12.618(2), c = 14.809(3) ?, β = 105.695(2)°, V = 2330.0(8) ?3, Z = 4, ρ c = 1.800 mg/m3, μ = 2.765 mm−1, F(000) = 1276, R = 0.0297, and wR = 0.0638 for 18416 observed reflections with I ≥ 2σ(I). One remarkable feature of the two complexes is that the protonated [EnH22+] cations conjugating to [EuIII(Ttha)]26− and [EuIII(Egta)(H2O)]22− complex anions are reviewed, respectively, which open the path for the EuIII complexes conjugating with other various biomolecules.  相似文献   

10.
11.
Single crystals of Cs4[(UO2)2(C2O4)(SO4)2(NCS)2] · 4H2O (I) and (NH4)4[(UO2)2(C2O4)(SO4)2(NCS)2] · 6H2O (II) have been synthesized and studied by X-ray diffraction. The crystals of both compounds are orthorhombic with the space group Pbam, Z = 2, and unit cell parameters a = 12.0177(3) ?, b = 18.6182(5) ?, c = 6.7573(10) ?, R = 0.0376 (I); a = 11.6539(9) ?, b = 18.3791(13) ?, c = 6.7216(5) ?, R = 0.0179 (II). The main structural units of crystals I and II are [(UO2)2(C2O4)(SO4)2(NCS)2]4− chains belonging to the crystal-chemical group A2K02B22M21 (A = UO22+, K02 = C2O42−, B2 = SO42−, M1 = NCS) of the uranyl complexes. The uranium-containing chains are joined into a three-dimensional framework due to a system of electrostatic interactions with the cesium or ammonium ions in the structure of I. In the structure of II, this framework is additionally stabilized by hydrogen bonds involving the outer-sphere water molecules and ammonium ions. Original Russian Text ? I.V. Medrish, A.V. Virovets, E.V. Peresypkina, L.B. Serezhkina, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 7, pp. 1115–1120.  相似文献   

12.
13.
The title dimanganese complexes react with NO (5% in N2) at room temperature to give as major products the corresponding hexanitrosyl derivatives [Mn2(NO)6(μ-L2)] in moderate yields, and they react rapidly with NO2 to give the corresponding hydride derivatives [Mn2(μ-H)(μ-NO2)(CO)6(μ-L2)], these having a nitrite ligand bridging the dimetal centre through the N and O atoms. The dppm-bridged dihydride also reacts selectively at 273 K with (PPN)NO2 to give first the nitro derivative (PPN)[Mn2(μ-H)(H)(NO2)(CO)6(μ-dppm)], which then transforms into the nitrosyl complex (PPN)[Mn2(μ-CO)(CO)5(NO)(μ-dppm)] at room temperature or above (dppm = Ph2PCH2PPh2; PPN+ = [N(PPh3)2]+). The latter anion reacts with (NH4)PF6 to give the hydride-bridged nitrosyl complex [Mn2(μ-H)(μ-NO)(CO)6(μ-dppm)] and with [AuCl(PPh3)] to give the trinuclear cluster [AuMn2(μ-NO)(CO)6(μ-dppm)(PPh3)] (Mn-Au = ca. 2.68 Å; Mn-Mn = 2.879(2) Å). Both products are derived from the addition of the added electrophile at the intermetallic bond and rearrangement of the nitrosyl ligand into a bridging position. In contrast, methylation of the anion with CF3SO3Me takes place at the nitrosyl ligand to yield the unstable methoxylimide derivative [Mn2(μ-NOMe)(CO)6(μ-dppm)]. Analogous reactions at the nitrosyl ligand take place upon the addition of HBF4·OEt2 to the nitrosyl-bridged hydrides [Mn2(μ-H)(μ-NO)(CO)n(μ-dppm)m] (n = 6, m = 1; n = 4, m = 2) to give the corresponding hydroxylimide derivatives [Mn2(μ-H)(μ-NOH)(CO)n(μ-dppm)m]BF4, which were also thermally unstable and could not be isolated nor fully characterized.  相似文献   

14.
A novel compound, [MnPhen3][(B9C2H11)Co(B8C2H10)Co(B9C2H11)]· CH3CN (Phen = 1,10-phenantroline), comprising a Co(III) dicobaltacarborane cluster anion has been prepared and characterized by single crystal X-ray diffraction. Crystal data are the following: C44H59B26N7Co2Mn, M = 1139.84, triclinic, space group , unit cell parameters: a = 13.2465(11) Å, b = 14.521(2) Å, c = 15.2536(15) Å; α = 77.027(9)°, β = 88.500(8)°, γ = 77.274(9)°; V = 2788.5(5) Å3, Z = 2, d calc = 1.358 g/cm3, T = 295 K, F(000) = 1162, μ = 0.853 mm−1. The structure was solved by the direct and Fourier methods and refined anisotropically (isotropically for hydrogen atoms) using the full-matrix technique to final factors R 1 = 0.0374, wR 2 = 0.0915 for 7397 I hkl ≥2σI of 9779 I hkl measured (diffractometer Enraf-Nonius CAD-4, λMoK α , graphite monochromator, θ/2θ-scanning). The structure is formed from [MnPhen3]2+ cations, [(B9C2H11)×Co(B8C2H10)Co(B9C2H11)]2− anions, and acetonitrile molecules CH3CN. Central Mn atom in the cation has a distorted octahedral coordination environment formed by six nitrogen atoms of three bi-dentate Phen ligands, average Mn-N bond length being 2.263(2) Å. The anion has a chain-like structure built from three icosahedra sharing common vertices occupied by the cobalt atoms. The central icosahedron including ten light atoms (8B, 2C) provides two vertices for the cobalt atoms shared with the other icosahedra having 11 light atoms (9B, 2C). The arrangement of-C2-groups in the anion corresponds to a quasi-gauche-configuration of asymmetric sandwich complexes of both cobalt atoms. Original Russian Text Copyright ? 2005 by T. M. Polyanskaya, V. V. Volkov, and M. K. Drozdova __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp.730–740, July–August, 2005.  相似文献   

15.
The title compound was synthesized by reaction of Cu(ClO4)2, picolinic acid and carbamide in C2H5OH/CH3CN solution, and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a=14.0481(8), b=9.0130(5), c=18.626(1)?, V=2358.3(2)?3Z=4, Dx=1.771g·cm-3, μ=1.235mm-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane, while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances, resulting in a 4+2 elongated octahedral environment. In the compound, there also exist two protonated carbamide cations for charge balance. CCDC: 195354.  相似文献   

16.
 Oxo peroxo glycolato complexes of vanadium(V) (M 2[V2O2(O2)2(C2H2O3)2nH2O (n=0, 1; M=NBu4 + (1), K+ (2), NH4 + (3), Cs+ (4), NPr4 + (5)) as well as (NBu4)2[V2O4(C2H2O3)2]ċ H2O (6) have been prepared and characterized by spectroscopic methods. X-Ray structure analysis of 1 revealed the presence of dinuclear [V2O2(O2)2(C2H2O3)2]2− anions with a (chemical structure) bridging core and six coordinated vanadium(V) atoms in a distorted pentagonal pyramidal array.  相似文献   

17.
The title compounds, (NH4)2[MnII(edta)(H2O)]·3H2O (H4edta = ethylenediamine-N,N,N′,N′-tetraacetic acid), (NH4)2[MnII(cydta)(H2O)]·4H2O (H4cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid) and K2[MnII(Hdtpa)]·3.5H2O (H5dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), were prepared; their compositions and structures were determined by elemental analysis and single-crystal X-ray diffraction technique. In these three complexes, the Mn2+ ions are all seven-coordinated and have a pseudomonocapped trigonal prismatic configuration. All the three complexes crystallize in triclinic system in P-1 space group. Crystal data: (NH4)2[MnII(edta)(H2O)]·3H2O complex, a = 8.774(3) ?, b = 9.007(3) ?, c = 13.483(4) ?, α = 80.095(4)°, β = 80.708(4)°, γ = 68.770(4)°, V = 972.6(5) ?3, Z = 2, D c = 1.541 g/cm3, μ = 0.745 mm−1, R = 0.033 and wR = 0.099 for 3406 observed reflections with I ≥ 2σ(I); (NH4)2[MnII(cydta)(H2O)]·4H2O complex, a = 8.9720(18) ?, b = 9.4380(19) ?, c = 14.931(3) ?, α = 76.99(3)°, β = 83.27(3)°, γ = 75.62(3)°, V = 1190.8(4)?3, Z = 2, D c = 1.426 g/cm3, μ = 0.625 mm−1, R = 0.061 and wR = 0.197 for 3240 observed reflections with I ≥ 2σ(I); K2[MnII(Hdtpa)]·3.5H2O complex, a = 8.672(3) ?, b = 9.059(3) ?, c = 15.074(6) ?, α = 95.813(6)°, β = 96.665(6)°, γ = 99.212(6)°, V = 1152.4(7) ?3, Z = 2, D c = 1.687 g/cm3, μ = 1.006 mm−1, R = 0.037 and wR = 0.090 for 4654 observed reflections with I ≥ 2σ(I). Original Russian Text Copyright ? 2008 by X. F. Wang, J. Gao, J. Wang, Zh. H. Zhang, Y. F. Wang, L. J. Chen, W. Sun, and X. D. Zhang The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 753–759, July–August, 2008.  相似文献   

18.
In this work, the title complexes, NH4[ErIII(Cydta)(H2O)2] · 4.5H2O (I) (H4Cydta = trans-1,2-cyclo-hexanediamine-N,N,N′,N′-tetraacetic acid) and (NH4)2[Er2III(Pdta)2(H2O)2] · 2H2O (II) (H4Pdta= propylene-diamine-N,N,N′,N′-tetraacetic acid), were prepared, respectively, and their composition and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques. Complex I selects a mononu-clear structure with pseudosquare antiprismatic geometry crystallized in the triclinic crystal system with space group $ P\bar 1 $ P\bar 1 and the central Er3+ ion is eight-coordinated by the hexadentate Cydta ligand and two water molecules. The crystal data are as follows: a = 8.568(3), b = 10.024(3), c = 14.377(4) ?, α = 88.404(4)°, β = 75.411(4)°, γ = 88.332(4)°, V = 1194.2(6) ?3, Z = 1, ρ c = 1.793 g/cm3, μ = 3.586 mm−1, F(000) = 648, R = 0.0257, and wR = 0.0667 for 4169 observed reflections with I ≥ 2σ(I). Complex II is eight-coordinated as well, which selects a binuclear structure with two pseudosquare antiprismatic geometry and crystallizes in the monoclinic crystal system with space group P21/n. The central Er3+ ion is coordinated by two nitrogens and four oxygens from one hexadentate Pdta ligand. Besides, two oxygens come from one carboxylic group of the neighboring Pdta ligand and one water molecule, respectively. The crystal data are as follows: a = 12.7576(8), b = 9.3151(6), c = 14.3278(9) ?, β = 96.1380(10)°, V = 1692.93(19) ?3, Z = 4, ρ c = 2.054 g/cm3, μ = 5.015 mm−1, F(000) = 1028, R= 0.0228, and wR = 0.0534 for 2984 observed reflections with I ≥ 2σ(I).  相似文献   

19.
The sandwich-type [Na(UO2)2(H2O)4(BiW9O33)2]13− uranium (VI) has been synthesized by reacting the trivacant species of B-α-[BiW9O33]9− with and investigated by IR and UV–Vis spectroscopy, and elemental analysis. The X-ray single crystal analysis was carried out on Na13[Na(UO2)2(H2O)4(BiW9O33)2] · 33H2O (I) which crystallizes in the orthorhombic system, space group Pna21 with a = 33.8454(19) ?, b = 21.1484(12) ?, c = 13.2403(7) ?, α = 90°, β = 90°, γ = 90°, and Z = 4. The polyanion consists of two lacunary B-α-[BiW9O33]9− groups which sandwich two uranyl cations and one sodium cation. The uranium atoms adopt distorted pentagonal–bipyramidal coordination, achieved by two equatorial bonds to each BiW9O33 unit and one external water ligand. The coordination of each uranium atom is evident by the shift of νas(W–Ob–W) and νas(Bi–O) stretching vibrational bonds. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

20.
Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C6H4-CH(OCH2)2]4 (2), which was transformed to Sn[C6H4-CHO]4 (3) and its hydrazido and amino derivatives Sn[C6H4-CHN-NH-C6H3-2,4-(NO2)2]4 (5) and Sn{C6H4-CH[N(C2H4)2O]2}4 (8). Oxidation of (3) produced Sn[C6H4-COOH]4 (4) while reduction of (3) gave Sn[C6H4-CH2-OH]4 (6). From the acid 4, an amino acid Sn[C6H4-CO-NH-CH2-CO-OCH3]4 (7) could be obtained by reaction with the methyl ester of glycine. All compounds were isolated in pure form with yields of 40-64% and were characterised by spectroscopic means (heteronuclear NMR) or by X-ray structure determination (3).  相似文献   

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