二硫代酯的单晶结构及荧光性能的研究(英文)

合成了两种单晶化合物二硫代酯1 和2,并对其经行了表征.二硫代酯1属于单斜晶系,空间群是P21/n; 二硫代酯2属于正交晶系,空间群是Pbca.此外,分别研究了两种二硫代酯在液态和固态中的荧光性能,发现二硫代酯1和2在乙腈溶剂中有很强的荧光,而在固体状态下没有荧光.这可能是由于在固态下分子间的堆积造成了荧光团发生迅速的π-π碰撞,从而导致荧光的自身淬灭.     

Synthesis, crystal structures, and electrochemical studies of ferrocenyl heterocyclic carbonylhydrazone receptors

Two new novel ferrocenylaclyhydrazone-based receptors FcL₁ and FcL₂ were prepared and characterized by ¹H NMR, IR, elemental analysis. X-ray crystallographic reveals that FcL₁ belongs to Monoclinic system, with space group P2(1)/c, and FcL₂ belongs to Hexagonal system with space group P6(5). It forms a novel helical chain by self-assembly. The electrochemical studies reveal that the formal potential (E ⁰) of FcL₁ and FcL₂ show a gradual decrease in the order Fc(Ferrocene) < FcL₁ < FcL₂ and FcL₁ is responsive to Pb²⁺. The maximum electrochemical shift of FcL₁ for Pb²⁺ is about 44 mV. FcL₁ shows selective potential response to Pb(II) ion.     

Synthesis, crystal structures, and photophysical properties of homodinuclear lanthanide xanthene-9-carboxylates

Three new homodinuclear lanthanide(III) complexes of xanthene-9-carboxylic acid, [Ln2(XA)6(DMSO)2(H2O)2](Ln = Eu (1), Tb (2) and Gd (3); HXA = xanthene-9-carboxylic acid; DMSO = dimethylsulfoxide), have been synthesized, of which 1 and 2 were structurally characterized by single-crystal X-ray diffraction. These compounds crystallize in the monoclinic space group P21/n with a =17.849(4) A, b = 9.6537(19) A, c = 23.127(5) A, beta = 109.06(3) degrees , and V = 3766.5(13) A3 for 1 and a =17.809(4) A, b = 9.6548(19) A, c = 23.075(5) A, beta = 108.97(3) degrees , and V = 3752.1(13) A3 for 2. The crystal structures of 1 and 2 consist of homodinuclear species that are bridged by two oxygen atoms from two carboxylate ligands. The two lanthanide ions are related by a center of inversion. Each lanthanide ion is coordinated by eight oxygen atoms in an overall distorted square-prismatic geometry. Six of the oxygen atoms are furnished by the carboxylate moieties, and the remaining two oxygen atoms are provided by water and DMSO molecules. The photophysical properties of these complexes in the solid state at room temperature have been investigated. The quantum yields were found to be 0.06 +/- 0.01 and 7.30 +/- 0.73% for 1 and 2, respectively.     

Synthesis and crystal structures of 1,2-diaminobenzene-Ni complexes

Treatment in different proportions of 1,2-diaminobenzene with Ni(OAc)₂ · 4H₂O in methanol results in the formation of two 1,2-diaminobenzene-Ni complexes I (C₉₂H₁₃₄N₂₄Ni₉O₂₈) and II (C₁₆H₂₂N₄NiO₄). Their structures were determined by X-ray diffraction analysis. The complexes are also characterized by elemental analysis and IR.     

3-乙酰基取代吡咯衍生物的合成及其晶体结构

本文通过Knorr合成法制备了四个3-位乙酰基取代的吡咯衍生物:1, 2-二甲基-4-异丙基-5-苯基-3-乙酰基-吡咯(5a); 1, 2, 4-三甲基-5-对甲氧苯基-3-乙酰基-吡咯(5b); 1, 2, 5-三甲基-4-苯基-3-乙酰基-吡咯(5c); 1, 2, 5-三甲基-4-对甲氧苯基-3-乙酰基-吡咯(5d)。通过红外, 质谱, 核磁等方法对其结构进行了表征。测定了其中三个化合物的晶体结构。对这类吡咯环上4或5-位有芳环取代基时化合物的晶体结构特征进行了扼要讨论, 晶体衍射实验结果表明,4, 5-位上的芳环与吡咯环本身处于非共平面结构。     

Synthesis and characterization of fluorescent acenequinones as dyes for guest-host liquid crystal displays

Syntheses and spectroscopic properties of alkoxy-substituted para-acenequinones are reported. These compounds showed excellent alignment in nematic liquid crystals as evidenced by polarized UV-vis absorption and fluorescence measurements. [structure: see text]     

簇外环化镍十硼烷簇合物的合成与结构研究

研究了[NiCl~2(PPh~3)~2],B~1~0H~1~0^2^-与硫代苯甲酸的反应,得到四个簇合物,其中三个簇合物[(PPh~3)(PhCOS)~2Ni·B~1~0H~1~0]·0.5C~6H~1~4(1),[(PhCOS)~2NiB~1~0H~8(PPh~3)](2),[(PhCOS)~3NiB~1~0H~7(PPh~3)](3)。通过单晶X射线衍射进行了结构研究。三个簇合物均为十一顶巢式构型,并分别存在两个、两个、三个簇外环化的五元环,具有三个环的簇合物至今未见其它文献报道。结构分析表明：簇外环化可以增强Ni－B之间的成键作用。     

Synthesis and crystal structures of two structurally related kryptoracemates

Kryptoracemates are racemic compounds (pairs of enantiomers) that crystallize in Sohnke space groups (space groups that contain neither inversion centres nor mirror or glide planes nor rotoinversion axes). Thus, the two symmetry‐independent molecules cannot be transformed into one another by any symmetry element present in the crystal structure. Usually, the conformation of the two enantiomers is rather similar if not identical. Sometimes, the two enantiomers are related by a pseudosymmetry element, which is often a pseudocentre of inversion, because inversion symmetry is thought to be favourable for crystal packing. We obtained crystals of two kryptoracemates of two very similar compounds differing in just one residue, namely rac‐N‐[(1S ,2R ,3S )‐2‐methyl‐3‐(5‐methylfuran‐2‐yl)‐1‐phenyl‐3‐(pivalamido)propyl]benzamide, C₂₇H₃₂N₂O₃, (I), and rac‐N‐[(1S ,2S ,3R )‐2‐methyl‐3‐(5‐methylfuran‐2‐yl)‐1‐phenyl‐3‐(propionamido)propyl]benzamide dichloromethane hemisolvate, C₂₅H₂₈N₂O₃·0.5CH₂Cl₂, (II). The crystals of both compounds contain both enantiomers of these chiral molecules. However, since the space groups [P 2₁2₁2₁ for (I) and P 1 for (II)] contain neither inversion centres nor mirror or glide planes nor rotoinversion axes, there are both enantiomers in the asymmetric unit, which is a rather uncommon phenomenon. In addition, it is remarkable that (II) contains two pairs of enantiomers in the asymmetric unit. In the crystal, molecules are connected by intermolecular N—H…O hydrogen bonds to form chains or layered structures.     

Synthesis and crystal structures of cyclopentadienyl dimolybdenum carbonyl complexes

Reactions of the fulvenes C₅H₄C(R ₁ R ₂) [(R ₁ = CH₂CH₃, R ₂ = CH₃ (1); R ₁ = R ₂ = C₂H₅ (2); R ₁, R ₂ = (CH₂)₄ (3), R ₁,R ₂ = (CH₂)₅ (4)] with Mo(CO)₆ in refluxing xylene gave the corresponding cyclopentadienyl dimolybdenum carbonyl complexes [(η⁵-C₅H₄CR₁′R₂′Mo(CO)₃]₂ [(R ₁′ = CH₂CH₃, R ₂′ = CH₃ (5); R ₁′ = R ₂′ = C₂H₅ (6); R ₁′, R ₂′ = CH(CH₂)₃ (7); R ₁′, R ₂′ = CH(CH₂)₄ (8)], which were characterized by elemental analysis, IR and ¹H NMR spectra. The molecular structures were determined by single-crystal X-ray diffraction. The results indicated the exocyclic double bond of the ligands 1 and 2 changed into a single bond and the exocyclic double bond of the ligands 3 and 4 underwent a double-bond isomerization process.     

Synthesis and X-ray crystal structures of some isothiosemicarbazone complexes

Transition Metal Chemistry - Four complexes of a new isothiosemicarbazone ligand have been prepared and characterized as μ2-pip-(NiL)2 (1), MnL2 (2), UO2L(BrSal)BuOH (3) and (μ2-MoO2L)2...     

分化诱导剂的合成及晶体结构

合成出四个分化诱导剂,N,N,N',N'-四乙酰已二胺(Ⅰ),1,6-二烟酰已二胺(Ⅱ),1,6-二(3,5-二氧哌嗪)已烷(Ⅲ)和1,6-二[3,3'-(5,5-二甲乙内酰脲)]已烷(Ⅳ),对合成方法和路线进行了优化,通过元素分析、质谱、核磁和红外进行了表征,测定了化合物Ⅲ对人白血病细胞的分化诱导活性,利用单晶X射线四圆衍射测定了化合物Ⅳ的晶体结构,并与化合物Ⅰ,Ⅱ,Ⅲ的晶体结构进行了比较。     

Synthesis and crystal structures of anhydrous lithium and ammonium hypophosphites

Conditions of synthesis (temperature, precursors) have been selected to grow crystals of anhydrous lithium and ammonium hypophosphites. The crystal structure of LiH₂PO₂ has been determined. Cell parameters and atomic positions in (NH₄)H₂PO₂ at room temperature and at 100 K have been refined. By their oxygen atoms the hypophosphite anions serve to bridge the four cations. Each oxygen atom is bonded to two cations, creating puckered layers parallel to the (001) planes. The structures show much similarity in the general arrangement, but differ in the type of the tetrahedral cation-anion bonds. In LiH₂PO₂, the Li-O bond is ionic (1.933(4) Å); in (NH₄)H₂PO₂, N-H...O is a hydrogen bond (2.846(1) Å).Original Russian Text Copyright © 2004 by M. I. Naumova, N. V. Kuratieva, D. Yu. Naumov, and N. V. PodberezskayaTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 491–496, May–June 2004.     

Synthesis and crystal structures of new palladium catalysts for the hydromethoxycarbonylation of alkenes

The preparation and structural characterization of dimeric Pd(I)-Pd(I) complex [Pd₂{(PPh₃)(OSO₂CF₃)}₂].CH₂Cl₂ (1) and three palladium center [Pd₃{(PPh₃)(OSO₂CF₃)}₂] (2) and [Pd₃(PPh₃)₄](SO3CF₃)₂ (3) complexes are reported. The complexes exhibit coordination in which the phosphine phenyl ring is used to stabilize Pd(I) centers in (1) and, Pd(I) and Pd(0) centers in (2) and (3) by acting as π electron donors. The complexes were characterized by single crystal X-ray crystallography.     

Synthesis and crystal structures of novel glycoluril carboxylic acids conglomerates

The two novel conglomerates were obtained by crystallization of racemic (2'S,3aS,6aR)/(2'R,3aR,6aS) (glycoluril-1-yl)-3-methylbutanoic acid and (2'R,3aR,6aR)/(2'S,3aS,6aS) (4,6-dimethylglycoluril-1-yl)pentanoic acid synthesized by highly diastereoselective condensation of 4,5-dihydroxy- imidazolidin-2-ones with racemic ureido acids. The differences in the molecular geometry of synthesized racemates were studied by X-ray diffraction that showed them to crystallize as conglomerates in non-centrosymmetric space groups Pna2₁ and P2₁2₁2₁, respectively     

Synthesis of two novel cobalt complexes and their crystal structures

Two new cobalt complexes were successfully synthesized from the reaction of binaphthyl Schiff base 2 with Co(OAc)₂ in the presence of sodium methoxide at 80 °C for 24 h and Co(acac)₃ in toluene under reflux. Their unique crystal structures are unambiguously disclosed by X‐ray analysis. Complex 3 is triclinic, space group P1 , unit cell dimensions a = 10.742(2) Å, b = 11.153(2) Å, c = 12.715 Å, α = 79.865(3) °, β = 76.053 °, γ = 72.532(4) °, volume 1401.3(5) ų, Z = 2. Complex 4 is triclinic, space group P1 , unit cell dimensions a = 10.801(2) Å, b = 12.554(3) Å, c = 15.219(3) Å, α = 105.672(4) °, β = 103.048 °, γ = 104.594(4) °, volume 1824.8(7) ų, Z = 2, calculated density 1.428 Mg m⁻³. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis and crystal structures of two hetarylazo indole disperse dyes

Two new heterocyclic monoazo disperse dyes were prepared by diazotizing 2-amino-5-methylthiazole and ethyl-1-(2-aminothiazol-4-yl)acetate and coupling with 1,2-dimethyl-indole. Characterization of the dyes was carried out by using UV–vis, FTIR, ¹H-NMR and MS spectroscopic techniques. The structures of the dyes have been determined by single-crystal X-ray diffraction method. The maximum absorption peaks (λ_max) in the ultraviolet and visible (UV–vis) spectra of the hetarylazoindole dyes have been determined by using the density-functional (DFT method) and time-dependent density-functional (TD-DFT method) theories. Excellent agreement was found between the calculated and experimental λ_max values.     

Synthesis and crystal structures of halogenated oxathiazolones and an unexpected propanamide

The known 1,3,4-oxathiazol-2-ones with crystal structures reported in the Cambridge Structural Database are limited (13 to date) and this article expands the library to 15. In addition, convenient starting materials for the future exploration of 1,3,4-oxathiazol-2-ones are detailed. An unexpected halogenated propanamide has also been identified as a by-product of one reaction, presumably reacting with HCl generated in situ. The space group of 5-[(E)-2-chloroethenyl]-1,3,4-oxathiazol-2-one, C₄H₂ClNO₂S, ( 1 ), is P2₁, with a high Z′ value of 6; the space group of rac-2,3-dibromo-3-chloropropanamide, C₃H₄Br₂ClNO, ( 2 ), is P2₁, with Z′ = 4; and the structure of rac-5-(1,2-dibromo-2-phenylethyl)-1,3,4-oxathiazol-2-one, C₁₀H₇Br₂NO₂S, ( 3 ), crystallizes in the space group Pca2₁, with Z′ = 1. Both of the structures of compounds 2 and 3 are modeled with two-component disorder and each molecular site hosts both of the enantiomers of the racemic pairs (S,S)/(R,R) and (R,S)/(S,R), respectively.     

Syntheses,crystal structures and fluorescent properties of imidazole based mixed-ligand nickle and cadmium complexes

Four novel mixed-ligand nickle and cadmium complexes [Cd(tolu)₂(imi)₃] (1) [CdCl₂(imi)₂]_n (2), [Ni(imi)₆](tolu)₂ (3) and [Ni(mand)₂(imi)₂]·H₂O (4) (imi = imidazole, Htolu = o-toluic acid, Hmand = mandelic acid) were synthesized and isolated in solid state based on nickle and cadmium salts, imidazole and different carboxylic acids. These complexes were characterized by FT-IR, elemental analyses, thermogravimetric (TG) analyses, UV–vis, X-ray structural analyses and fluorescence spectra. Complexes 1 and 4 are neutral mixed-ligand molecules. Complex 2 exhibits a 2D chain constructed by [CdCl₂(imi)₂] units. Complex 3 possesses [Ni(imi)₆]^2- anions with uncoordinated tolulate anions. In complexes 1–4, each imidazole ligand provides one nitrogen atom for coordination. Tolulate and mandelate ligands coordinate to the metal through carboxyl oxygen or hydroxyl oxygen atoms. Plenty of intramolecular hydrogen bonds as N–H?O and O–H?O interactions are observed in these complexes. Fluorescence properties of the complexes have been deeply investigated and the result reveals that Fe³⁺ ion has the greatest effect on fluorescence intensity of complex 3. The fluorescence intensity decreases with the increase of iron concentration.     

Synthesis and crystal structures of novel lithium- and palladium-1-azaallyls

Treatment of (RH₂C)₂C₅H₃N-2,6 (R=SiMe₃) with BuⁿLi followed by addition of Me₃SiCl gave the tetrasilyl pyridine derivative (R₂HC)₂C₅H₃N-2,6 1 in high yield. Further lithiation of 1 with BuⁿLi and reaction of the intermediate with PhCN led to the new lithium-1-azaallyl [Li{N(R)C(Ph)C(R)(C₅H₃N-2,6)(CHR₂)}]₂2, while metallation of the previously described di-lithium compounds [Li{N(R)C(R^′)CH}₂(C₅H₃-2,6)]Li(tmen)_n (R=SiMe₃, R^′=Bu^t, n=1 or R=SiMe₃, R^′=Ph, n=2) with PdCl₂(PhCN)₂ yielded the novel metallacycles [Pd{{N(H)(R)C(R^′)CH}{N(SiMe₂CH₂)C(R^′)CH}C₅H₃N-2,6}] 3 (R^′=Bu^t) and [Pd{{N(R)C(R^′)CH}{N(R)(H)C(R^′)CH}C₅H₃N-2,6}₂] (R^′=Ph) 4 in moderate to low yield. Compound 3 is unusual in being the first example of a crystallographically characterised PdNSiC heterocycle which is believed to be formed via an intramolecular CH-activation of a trimethylsilyl group by Pd(II). All four compounds were fully characterised by NMR-spectroscopy, microanalysis (not 4) and X-ray diffraction.