含硫、氮Schiff碱配合物—二水二分之一二甲基亚砜醋酸四邻香草醛缩胺基硫脲合镉(Ⅱ)的合成及晶体结构

X射线单晶衍射结果表明,三核镉配合物Cd₃[CH₃O(O)C₆H₃CH=NNHC(S)NH₂]4·[CH₃COO]₂·1/2[CH₃S(O)CH₃]·2H₂O为单斜晶系,空间群为C2/c,a=3.4214(4),b=1.1581(2),c=1.7932(5)nm,β=119.76(1)°,V=6.168nm³,Mr=1427.43,Z=4,D_c=1.54g/cm³,μ=12.48cm^-1,F(000)=2860,最后偏离因子R=0.066.     

有机-无机杂化磷酸锆及胺插层化合物的MAS NMR 研究

The layered zirconium [N-(phosphonomethyl)iminodiacetic acid-phosphate] Zr(HPO₄)_1.34[O₃PCH₂N-(CH₂CO₂H)2]_0.66·H₂O can only be prepared in the series of the zirconium phosphonate-phosphates Zr(HPO₄)_2-x[O₃PCH₂N(CH₂CO₂H)₂]_x·H2O (ZPPMIDA) by the reaction of zirconium oxychloride with phosphonic acid and H₂O₃PCH₂N(CH₂CO₂H)₂ in the designed x range of 0 < x < 2, which had been monitored by using the phosphorus integration value ratio of HPO₄^2- and [O₃PCH₂N(CH₂CO₂H)₂]^2- group in the ³¹P MAS NMR spectra. After intercalation of n-butyl amine, the ³¹P chemical shift of HPO₄^2- group at -8.0~-10.0 ppm moved to 6.0 ppm with a change of 14.0~16.0 ppm and that of [O₃PCH₂N(CH₂CO₂H)₂]^2- group at -29.1 ppm changed only 0.5 ppm. Due to the pillared effect of [O₃PCH₂N(CH₂CO₂H)₂]^2- groups on the interlayer spacing, intercalated amines such as n-butylamine, n-hexyl amine and n-octyl amine easily reacted with HPO₄^2- group in ZPPMIDA (x=0.66) rather than that in α-ZrP, and carboxylic group (-CO₂H) in ZPPMIDA (x=0.66).     

两种含有十二元环的层状稀土硫酸盐的合成、结构表征及性质研究

通过溶剂热合成技术,我们得到了两种新的二维层状稀土硫酸盐:[Tb₂(SO₄)₅][(CH₃)₂NH₂]₄(1)和[Y₂(SO₄)₅][(CH₃)₂NH₂]₄(2),并通过X-射线衍射、元素分析及红外、热重对化合物进行了表征。两种化合物都属于三斜晶系,P1空间群。其中化合物1:a=0.9887(3)nm,b=1.1061(3)nm,c=1.5354(4)nm,α=70.45(0)°,β=75.12(0)°,γ=67.11(0)°,Z=2;化合物2:a=0.9816(5)nm,b=1.1001(5)nm,c=1.5286(8)nm,α=70.44(1)°,β=75.45(1)°,γ=67.48(1)°,Z=2。通过对晶体结构进行表征我们发现两种化合物都含有二维层状无机骨架结构,该层由2种不同类型的双链和十二元环构成。我们还对化合物1的荧光性质进行了研究,其在369nm的激发波长下表现出了Tb³⁺ 的特征发射。     

两种含有十二元环的层状稀土硫酸盐的合成、结构表征及性质研究

通过溶剂热合成技术,我们得到了两种新的二维层状稀土硫酸盐：[Tb₂(SO₄)₅][(CH₃)₂NH₂]₄(1)和[Y₂(SO₄)₅][(CH₃)₂NH₂]₄(2),并通过X-射线衍射、元素分析及红外、热重对化合物进行了表征。两种化合物都属于三斜晶系,P1空间群。其中化合物1：a=0.988 7(3) nm,b=1.106 1(3) nm,c=1.535 4(4) nm,α=70.45(4)°,β=75.12(3)°,γ=67.11(3)°,Z=2;化合物2：a=0.981 6(5) nm,b=1.100 1(5) nm,c=1.528 6(8) nm,α=70.44(6)°,β=75.45(6)°,γ=67.48(6)°,Z=2。通过对晶体结构进行表征我们发现两种化合物都含有二维层状无机骨架结构,该层由2种不同类型的双链和十二元环构成。我们还对化合物1的荧光性质进行了研究,其在369 nm的激发波长下表现出了Tb³⁺的特征发射。     

(NH2CH2CH2NH3)4[WⅤO2(OC6H4O)2]2(NH3CH2CH2NH3)·H2O的合成、晶体结构、EPR以及与同构物的比较

Cis-dioxo-catecholatotungsten(Ⅴ) complex (NH₂CH₂CH₂NH₃)₄[W^ⅤO₂(OC₆H₄O)₂]₂(NH₃CH₂CH₂NH₃)·H₂O (1) was synthesized at room temperature by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH₃OH, CH₃CN and NH₂CH₂CH₂NH₂. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/c,a=0.712 8(3) nm, b=3.082 3(11) nm, c=0.982 8(4) nm, β=102.639(6)°, V=2.106 8(14) nm³, Z=2, R₁=0.062 8, wR₂=0.183 7. Compared the complex with its analogous complexes (NH₂CH₂CH₂NH₃)₃[Mo^ⅤO₂(OC₆H₄O)₂], it is found that the coordination structure of W have no changes in the processing of electron transfer of tungsten-containing enzymes from the result of the similarity of the EPR spectra of the complexes and flavoenzyme from milk. CCDC: 272937.     

三种马来二腈基二硫烯镍(Ⅲ)离子对配合物的制备和结构表征

合成了3种离子对配合物 [1-benzyl-3-bromopyridium]⁺[Ni(mnt)₂]^- (1)，[1-(4′-flurobenzyl)-3-bromopyridiunm]⁺[Ni(mnt)₂]^- (2)，[1-(4′-cholorobenzyl)-3-bromopyridium]⁺[Ni(mnt)₂]^- (3)，(mnt=马来二腈基二硫烯，maleonitrile dithiolate)获得了单晶并解析了它们的单晶结构。     

Transformations of high spin MnII and FeII polymeric pivalates in reactions with pivalic acid and o-phenylenediamines

The thermolysis and reactions of the polymeric high spin Mn^II and Fe^II complexes [Mn(μ-OOCBu^t)₂(HOEt)]_n (1) and [Fe(μ-OOCBu^t)₂]_n (3) with pivalic acid and o-phenylenediamines 1,2-(NH₂)₂C₆H₂R₂ (R = H or Me) were studied. The synthesis of compound 1 performed with a deficiency of pivalate anions affords the antiferromagnetic chloropivalate polymer { (MeCN)(HOOCBu^t)(H₂O)Mn₅Cl(OH)(OOCBu^t)₈·MeCN}_n. The reaction of 1 with an excess of pivalic acid produces the antiferromagnetic polymer [Mn₄(OOCBu^t)₈(HOOCBu^t)₂]_n. The analogous reaction of pivalic acid with polymer 3 gives the mononuclear complex Fe(η ¹-OOCBu^t)₂(η¹-HOOCBu^t)₄ containing the high spin iron(II) atom as the major product. Study of the reactions of 3 with a deficiency (<1: 1) and an excess (>1: 1) of diamines demonstrated that the polymer {[(η²-(NH₂)₂C₆H₄)₂Fe(μ-OOCBu^t)₂][Fe₂(μ-OOCBu^t)₄] · · 2MeCN}_n is generated as the major product in the former case, whereas the mononuclear complexes Fe(η¹-OOCBu^t)₂[η¹-(NH₂)₂C₆H₄]₄ and Fe(η¹-OOCBu^t)₂[η²-(NH₂)₂C₆H₂Me₂][η¹-(NH₂)₂C₆H₂Me₂]₂ are predominantly obtained in the latter case. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 779–792, May, 2006.     

[Me3NC2H4OH]Zn2Cl5水溶液的激光光解研究

利用时间分辨激光光解技术研究了季铵盐型离子液体[Me₃NC₂H₄OH]Zn₂Cl₅(简写R-Zn₂Cl₅)的光解行为, 研究发现离子液体能被266 nm激光单光子电离, 生成阳离子自由基、[Zn₂Cl₅]^•中性自由基和水合电子, 观察到胆碱激发三线态的存在, 并测定了离子液体光电离的量子产额为0.04. 利用266 nm激光对离子液体、胆碱、氯化锌、氯化钠的光解行为比较, 发现胆碱阳离子的贡献很小, [Zn₂Cl₅]^－阴离子起主要作用. 采用氧化性自由基SO₄^•－引发离子自由基, 揭示其光电离机理, 测定离子液体的动力学反应速率常数, SO₄^•－ 460 nm的衰减速率常数为1.3×10⁹ L•mol^－1•s^－1, 320 nm离子自由基瞬态产物的生成速率常数为1.5×10⁹ L•mol^－1•s^－1, 两者很接近, 说明SO₄^•－自由基的衰减与瞬态自由基的生成是同步的.     

第二结构导向剂诱导形成的二维有机模板稀土硫酸盐

水热条件下合成了具有超大孔道和层状结构的有机模板稀土硫酸盐。超大孔道的稀土硫酸盐（1）的分子式为[（CH₃）₂NH₂]₉[Pr₅（SO₄）₁₂]·2H₂O,它展现出有趣的交叉二十元环孔道结构。层状的稀土硫酸盐的分子式为[H₃O]₃[（CH₃）₂NH₂]₃[Ln₂（SO₄）₆]（Ln=Pr,2;Nd,3）,它可以被看作是由双链和八元环结合而成。这3种化合物的合成揭示了大的有机胺（三聚氰胺）可能用作为第二结构导向剂,阻止形成高维数的无机骨架,从而诱导了二维层状结构稀土硫酸盐晶体的生长。对化合物1和3的磁性进行了研究,测试的温度范围在2~300 K。     

第二结构导向剂诱导形成的二维有机模板稀土硫酸盐

水热条件下合成了具有超大孔道和层状结构的有机模板稀土硫酸盐。超大孔道的稀土硫酸盐（1）的分子式为[（CH₃）₂NH₂]₉[Pr₅（SO₄）₁₂]·2H₂O,它展现出有趣的交叉二十元环孔道结构。层状的稀土硫酸盐的分子式为[H₃O]₃[（CH₃）₂NH₂]₃[Ln₂（SO₄）₆]（Ln=Pr,2;Nd,3）,它可以被看作是由双链和八元环结合而成。这3种化合物的合成揭示了大的有机胺（三聚氰胺）可能用作为第二结构导向剂,阻止形成高维数的无机骨架,从而诱导了二维层状结构稀土硫酸盐晶体的生长。对化合物1和3的磁性进行了研究,测试的温度范围在2~300 K。     

Crystallographic report: A two‐dimensional zinc phosphate framework: [H3N(CH2)3NH3]0.5[Zn2(PO4)(HPO4)]

The two‐dimensional zinc phosphate [H₃N(CH₂)₃NH₃]_0.5[Zn₂(PO₄)(HPO₄)], has been synthesized hydrothermally using 1,3‐diaminopropane as the template. Its structure contains an inorganic framework with three‐, four‐, or six‐membered rings, built from PO₄, PO₃(OH) and ZnO₄ tetrahedral moieties sharing vertexes. The protonated 1,3‐diaminopropane molecules interact with the framework through hydrogen bonds. Copyright © 2004 John Wiley & Sons, Ltd.     

Template Syntheses of Two Open‐framework Zinc Phosphites

Two new open‐framework zincophosphites, Zn(H₆C₄N₂S)(HPO₃) (TJPU‐4) and [C₆N₂H₁₄]·[Zn₃(HPO₃)₄] (TJPU‐5) have been hydrothermally synthesized by using 2‐mercapto‐1‐methylimidazole [MMI] and 1,4‐diazabicyclo[2.2.2]octane [DABCO] as templates. TJPU‐4 crystallizes in monoclinic space group P2₁/c with the cell parameters a = 8.787(4) Å, b = 9.732(4) Å, c = 10.515(4) Å, β = 105.316(6)°, V = 867.3(6) ų. The structure of TJPU‐4 is constructed by ZnO₃S tetrahedron and HPO₃ pseudo‐pyramid to generate a layer of 4, 8‐network in bc plane. The organic template locates on the both sides of the 8‐membered rings and bonds to zinc atom through Zn–S bond. TJPU‐5 crystallizes in the triclinic space group with cell parameters a = 9.294 (5) Å, b = 9.976 (5) Å, c = 9.986 (5) Å, α = 85.692 (7)°, β = 82.010 (7)° and γ = 80.184 (7)°, V = 902.1 (8) ų. A novel 4⁴8⁸ cage is found in TJPU‐5. The connections of Zn(1)O₄, Zn(3)O₄ and HPO₃ groups give rise to an infinite corner‐shared four‐ring chain. Using Zn(2)O₄ as four connected bridges, linkages of these chains produce a 3‐D framework with intersecting 8‐ring channels running along [100], [010], [001], [011] and [111] directions.     

Structural Transformation of Three‐Dimensional Bimetallic Phosphites Containing Corner‐Sharing 4‐Ring Chains

Two open‐framework bimetallic phosphites, [C₆H₁₈N₂][Co_0.3Zn_2.7 (HPO₃)₄] ( 1 ) and [C₂H₈N]₂[Co_0.3Zn_2.7(HPO₃)₄] ( 2 ) were synthesized and characterized. The inorganic frameworks of the two compounds are constructed from strictly alternating MO₄ (M = Zn, Co)tetrahedra and HPO₃ pseudo pyramids, forming three‐dimensional networks with 8‐ring and 12‐ring channels for 1 and 16‐ring channels for 2 . The anionic frameworks of the two compounds can be easily transformed to a neutral framework structure with 16‐ring channels at room temperature.     

Hydrothermal synthesis and structural characterization of two organically templated zincophosphites with three-dimensional frameworks, (C6H14N2)·[Zn3(HPO3)4] and (C4H12N2)·[Zn3(HPO3)4]

Two organically templated zincophosphites, (C₆H₁₄N₂)·[Zn₃(HPO₃)₄] and (C₄H₁₄N₂)·[Zn₃(HPO₃)₄] have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction. (C₆H₁₄N₂)·[Zn₃(HPO₃)₄] crystallizes in the triclinic space group , with cell parameters, a=9.363(4) Å, b=10.051(4) Å, c=10.051(4) Å, α=85.777(13)°, β=82.091(9)°, and γ=79.783(9)°. (C₄H₁₄N₂)·[Zn₃(HPO₃)₄] crystallizes in the monoclinic space group P2₁/c, with cell parameters, a=9.9512(3) Å, b=10.1508(3) Å, c=17.8105(5) Å, and β=95.6510(10)°. Although the two structures are different, they have the same anionic framework compositions of [Zn₃(HPO₃)₄]²⁻. Their frameworks are built up from strictly alternating ZnO₄ tetrahedra and HPO₃ pseudo pyramids by sharing vertexes. There exist channels with an eight-membered ring window along the a- and c-axis. Powder X-ray diffraction, IR spectroscopy, ³¹P MAS solid-state NMR, thermogravimetric and differential thermal analyses were also carried out.     

Water‐Free Rare‐Earth‐Metal Ionic Liquids/Ionic Liquid Crystals Based on Hexanitratolanthanate(III) Anion

The hexanitratolanthanate anion (La(NO₃)₆^3?) is an interesting symmetric anion suitable to construct the component of water‐free rare‐earth‐metal ionic liquids. The syntheses and structural characterization of eleven lanthanum nitrate complexes, [C_nmim]₃[La(NO₃)₆] (n=1, 2, 4, 6, 8, 12, 14, 16, 18), including 1,3‐dimethylimidazolium hexanitratolanthanate ([C₁mim]₃[La(NO₃)₆], 1 ), 1‐ethyl‐3‐methylimidazolium hexanitratolanthanate ([C₂mim]₃[La(NO₃)₆], 2 ), 1‐butyl‐3‐methylimidazolium hexanitratolanthanate ([C₄mim]₃[La(NO₃)₆], 3 ), 1‐isobutyl‐3‐methylimidazolium hexanetratolanthanate ([isoC₄mim]₃[La(NO₃)₆], 4 ), 1‐methyl‐3‐(3′‐methylbutyl)imidazolium hexanitratolanthanate ([MC₄mim]₃[La(NO₃)₆], 5 ), 1‐hexyl‐3‐methylimidazolium hexanitratolanthanate ([C₆mim]₃[La(NO₃)₆], 6 ), 1‐methyl‐3‐octylimidazolium hexanitratolanthanate ([C₈mim]₃[La(NO₃)₆], 7 ), 1‐dodecyl‐3‐methylimidazolium hexanitratolanthanate ([C₁₂mim]₃[La(NO₃)₆], 8 ), 1‐methyl‐3‐tetradecylimidazolium hexanitratolanthanate ([C₁₄mim]₃[La‐(NO₃)₆], 9 ), 1‐hexadecyl‐3‐methylimid‐azolium hexanitratolanthanum ([C₁₆dmim]₃[La(NO₃)₆], 10 ), and 1‐methyl‐3‐octadecylimidazolium hexanitratolanthanate ([C₁₈mim]₃[La(NO₃)₆], 11 ) are reported. All new compounds were characterized by ¹H and ¹³C NMR, and IR spectroscopy as well as elemental analysis. The crystal structure of compound 1 was determined by using single‐crystal X‐ray diffraction, giving the following crystallographic information: monoclinic; P2₁/c; a=15.3170 (3), b=14.2340 (2), c=13.8954(2) Å; β=94.3453(15)°, V=3020.80(9) ų, Z=4, ρ=1.764 g cm^?3. The coordination polyhedron around the lanthanum ion is rationalized by six nitrate anions with twelve oxygen atoms. No hydrogen‐bonding network or water molecule was found in 1 . The thermodynamic stability of the new complexes was investigated by using thermogravimetric analysis (TGA). The water‐free hexanitratolanthanate ionic liquids are thermal and moisture stable. Four complexes, namely complexes 8 – 11 , were found to be ionic liquid crystals by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). They all present smectic A liquid‐crystalline phase.     

Characterization of Two Zincophosphates (UH‐6 and UH‐10) Synthesized using the Cobalt(III) Sarcophagine Complex as Structure‐directing Agent

The novel zincophosphates UH‐6 (sum formula |[Co(diAMHsar)]| [Zn₂(HPO₄)₃(PO₄)] · H₂O) and UH‐10 (sum formula |([Co(diAMHsar)])₂| [{Zn₂(HPO₄)₃(PO₄)}₂] · H₂O) were synthesized in hydrothermal syntheses employing the chiral sarcophagine complex [Co(diAMHsar)]⁵⁺ as the structure‐directing agent. The inorganic part of UH‐6 consists of pearl‐like chains of alternating [ZnO₄] and [PO₄] tetrahedra, which are connected to the incorporated cobalt complex via numerous hydrogen bonds. UH‐10 was synthesized under similar conditions, but at higher reaction temperatures. In consequence, the crystal structures of UH‐6 and UH‐10 are closely related, although systematic disorder in UH‐10 and the lower symmetry result in a unit cell twice as large as the corresponding unit cell of UH‐6. Interestingly, in both zincophosphates only one enantiomer of the cobalt complex is present, despite the fact that a racemic mixture of the complex salt is used for synthesis. Thermogravimetric analysis and powder X‐ray diffraction of a thermally treated sample of UH‐6 reveals a phase transformation at ca. 300 °C.     

Potassium,rubidium and ammonium salts of μ‐(formato‐κ2O:O′)‐μ‐oxido‐bis[oxidobis(peroxido‐κ2O,O′)molybdate(VI)]

The unit‐cell parameters of the three title salts, namely, tripotassium, K₃[Mo₂(CHO₂)O₃(O₂)₄], trirubidium, Rb₃[Mo₂(CHO₂)O₃(O₂)₄], and triammonium μ‐(formato‐κ²O:O′)‐μ‐oxido‐bis[oxidobis(peroxido‐κ²O,O′)molybdate(VI)], (NH₄)₃[Mo₂(CHO₂)O₃(O₂)₄], which were all crystallized at pH 3, are quite similar, but the potassium and rubidium salt structures are noncentrosymmetric, whereas that of the ammonium salt is centrosymmetric. Formate acts as an O:O′‐bridging ligand in the complex anion and is bound to a μ‐oxido‐bis(oxidodiperoxidomolybdate) unit.     

Guest‐Induced 2‐D Metallopolycapsular Networks Based on a 1,3‐Alternate Calix[4]arene Derivative

Solvothermal reactions of the calix[4]arene tetraacetic acid (H₄CTA) with zinc nitrate in the presence of α,ω‐diaminoalkanes afford two‐dimensional metallopolycapsular networks of the formula {[Me₂NH₂]₂[G@(Zn₂(CTA)₂)] ? (DMF)₂ ? (H₂O)₄}_n (G=⁺NH₃–(CH₂)_n–NH₃⁺, n=2, 3, 4; DMF=N,N‐dimethylformamide). These metallopolycapsular networks are built up of metallocapsules that consist of two CTA and two Zn^II ions. Short alkanediyldiammonium (⁺NH₃–(CH₂)_n–NH₃⁺, n=2, 3, 4) guest ions are accommodated in each capsule of the metallopolycapsular network through a variety of supramolecular interactions. The thermal behaviours and the solid‐state photoluminescent properties of these complexes were also investigated.     

A fourfold interpenetrating diamondoid three‐dimensional coordination polymer: poly[[[μ2‐1,2‐bis(pyridin‐4‐yl)ethene‐κ2N:N′](μ2‐5‐hydroxyisophthalato‐κ2O1:O3)zinc(II)] 1,2‐bis(pyridin‐4‐yl)ethene hemisolvate]

In the title compound, {[Zn(C₈H₄O₅)(C₁₂H₁₀N₂)]·0.5C₁₂H₁₀N₂}_n or {[Zn(HO‐BDC)(bpe)]·0.5bpe}_n [HO‐H₂BDC is 5‐hydroxyisophthalic acid and bpe is 1,2‐bis(pyridin‐4‐yl)ethene], the asymmetric unit contains a Zn^II atom, one HO‐BDC ligand, one coordinated bpe ligand and half a noncoordinating bpe molecule with crystallographic inversion symmetry. Each Zn^II centre is four‐coordinated by two O atoms from two distinct HO‐BDC ligands and two N atoms from two different bpe ligands in a ZnO₂N₂ coordination environment. The three‐dimensional topology of the title compound corresponds to a fourfold interpenetrating diamondoid coordination polymer network, with the uncoordinated bpe ligands located in the cavities, hydrogen bonded to the main network via the hydroxy group of the HO‐H₂BDC ligand.     

Crystallographic report: Bis{µ‐[O‐cyclopentyl(4‐methoxyphenyl) dithiophosphonato]1κ:S,2κ:S‐[O‐cyclopentyl(4‐methoxyphenyl)dithiophosphonato]1κ2S,S′} dizinc(II)

The centrosymmetric [Zn₂{CH₃OC₆H₄P(OC₅H₉)S₂}₄], features an eight‐membered Zn₂S₄P₂ ring as a result of two bidentate bridging thiolate ligands; the remaining ligands are chelating. Copyright © 2005 John Wiley & Sons, Ltd.