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1.
Jiang HL  Ma E  Mao JG 《Inorganic chemistry》2007,46(17):7012-7023
Solid-state reactions of lanthanide(III) oxide (and/or lanthanide(III) oxychloride), MoO3 (or WO3), and TeO2 at high temperature lead to eight new luminescent compounds with four different types of structures, namely, Ln2(MoO4)(Te4O10) (Ln = Pr, Nd), La2(WO4)(Te3O7)2, Nd2W2Te2O13, and Ln5(MO4)(Te5O13)(TeO3)2Cl3 (Ln = Pr, Nd; M = Mo, W). The structures of Ln2(MoO4)(Te4O10) (Ln = Pr, Nd) feature a 3D network in which the MoO4 tetrahedra serve as bridges between two lanthanide(III) tellurite layers. La2(WO4)(Te3O7)2 features a triple-layer structure built of a [La2WO4]4+ layer sandwiched between two Te3O72- anionic layers. The structure of Nd2W2Te2O13 is a 3D network in which the W2O108- dimers were inserted in the large tunnels of the neodymium(III) tellurites. The structures of Ln5(MO4)(Te5O13)(TeO3)2Cl3 (Ln = Pr, Nd; M = Mo, W) feature a 3D network structure built of lanthanide(III) ions interconnected by bridging TeO32-, Te5O136-, and Cl- anions with the MO4 (M = Mo, W) tetrahedra capping on both sides of the Ln4 (Ln = Pr, Nd) clusters and the isolated Cl- anions occupying the large apertures of the structure. Luminescent studies indicate that Pr2(MoO4)(Te4O10) and Pr5(MO4)(Te5O13)(TeO3)2Cl3 (M = Mo, W) are able to emit blue, green, and red light, whereas Nd2(MoO4)(Te4O10), Nd2W2Te2O13, and Nd5(MO4)(Te5O13)(TeO3)2Cl3 (M = Mo, W) exhibit strong emission bands in the near-IR region.  相似文献   

2.
Element-Element-Bonds. VI. Crystalline 2-Chloro-1,3,2-benzoxathiastibole – a Multiply Linked Coordination Polymer Yellow 2-chloro-1,3,2-benzoxathiastibole 4a first prepared by Anchisi and coworkers [3] from o-hydroxythiophenol and antimony trichloride, crystallizes in the monoclinic space group P21/n {a = 1109.9(3); b = 610.5(2); c = 1201.5(2) pm; β = 100.35(2)° at ?120 ± 3°C; Z = 4}. An X-ray structure determination (R = 0.029) shows the molecules to form coordination polymeric layers via Sb…?Cl, Sb…?O and Sb…?η2-arene interactions in the solid. Characteristic structural features are Sb? Cl…?Sb? Cl helices (Sb? Cl…?Sb 119°; Cl? Sb…?Cl 95°) and centrosymmetric, four membered Sb2O2-rings (O? Sb…?O 64°; Sb? O…?Sb 116°). The ligands set up a strongly distorted octahedron around the antimony atom: Sb? S 242; Sb? Cl 243; Sb…?Cl 328; Sb? O 201; Sb…?O 287; Sb…?C 338 and 341 pm; S? Sb? O 85°; S? Sb? Cl 94°; O? Sb? Cl 92°.  相似文献   

3.
Gao Q  Wang X  Jacobson AJ 《Inorganic chemistry》2011,50(18):9073-9082
A chiral cluster compound, dipotassium bis(μ-tartrato)diantimony(III), K(2)Sb(2)L(2) (H(4)L = L-tartaric acid), was used as a secondary building unit to react with lanthanide ions. Three series of homochiral coordination compounds were obtained: 0D [La(H(2)L)(H(2)O)(4)](2)[Sb(2)L(2)]·7H(2)O (0D-La), 1D Ln(Sb(2)L(2))(H(2)O)(5)(NO(3))·H(2)O (1D-Ln) (Ln = La-Lu or Y, expect Pm), 2D(I) [(Ln(H(2)O)(5))(2)(Sb(2)L(2))(3)]·5H(2)O (2D(I)-Ln) (Ln = La, Ce, Pr), and 2D(II) [(La(H(2)O)(5))(2)(Sb(2)L(2))(3)]·6H(2)O (2D(II)-La). Single-crystal X-ray diffraction studies indicated that 0D-La crystallizes in space group P1, and the structure contains isolated Sb(2)L(2)(2-) units located between chains of composition La(H(2)L)(H(2)O)(4). The series of 1D-Ln compounds is isostructural and crystallizes in space group P2(1)2(1)2(1). In the structure, Sb(2)L(2)(2-) units are coordinated to two Ln ions by two out of the four free tartrate oxygen atoms to form a linear chain. To the best of our knowledge, this is the first example of a homochiral structure that can be formed for the whole lanthanide series. In the 2D(I)-Ln structure series, which crystallizes in space group P2(1), the Sb(2)L(2)(2-) units have two distinct coordination modes: one is the same as that found in the 1D structure, while in the other all four free tartrate oxygen atoms are coordinated to four Ln ions in a very distorted tetrahedral arrangement. The connectivity between Sb(2)L(2)(2-) secondary units and LnO(9) polyhedra gives rise to infinite layers. 2D(II) [(La(H(2)O)(5))(2)(Sb(2)L(2))(3)]·6H(2)O, which crystallizes in space group C2, has a similar network to the 2D(I)-Ln compounds. The trends in lattice parameters, bond lengths, and ionic radii in the 1D-Ln series were analyzed to show the effect of the lanthanide contraction.  相似文献   

4.
以[(bpca)Fe(CN)3]-(bpca=二(2-吡啶羰基)酰胺阴离子)为构筑基元,设计合成了2个新颖的3d-4f异金属配合物,{[(bpca)Fe(CN)3Pr(H2O)5]Cl2}n(1)和{[(bpca)2Fe2(CN)6Pr(H2O)6]Cl·4H2O}n(2),并测定了它们的晶体结构.化合物1的晶体属正交晶系,Pnma空间群;而化合物2属三斜晶系,P1空间群.在这2个化合物中,[(bpca)Fe(CN)3]-和[Pr(H2O)x]3 (1,x=5;2,x=6)交替排列形成一维链状结构,并通过π-π堆积作用、氢键作用及分子间短距离相互作用形成三维网络结构.  相似文献   

5.
固固相反应合成牛磺酸水杨醛钾与锑、铋的配合物   总被引:2,自引:0,他引:2  
合成了牛磺酸水杨醛钾,并采用室温固固相反应法合成了牛磺酸水杨醛钾与三氯化锑和三氯化铋的配合物,其组成为:K2MC18H20O8N2S2 (M = Sb, Bi)。两种配合物的晶体结构均属于单斜晶系,锑配合物的晶胞参数为:a = 1.2869 nm, b = 1.7636 nm, c = 1.9917 nm, β= 93.79埃活榕浜衔锏木О问篴 = 1.4770 nm, b = 2.0334 nm, c = 2.0149 nm, β= 94.05。红外光谱表明N、Cl原子参与了配位,中心离子的配位数为5。  相似文献   

6.
A series of novel two-dimensional (2D) and three-dimensional (3D) praseodymium coordination polymers, namely, {[Pr3(PDA)4(HPDA)(H2O)8] x 8H2O}n (2), {[Pr2(PDA)3(H2O)3] x H2O}n (3), {[Pr(PDA)(H2O)4] x ClO4}n (4), and { [Pr2(PDA)2(H2O)5SO4] x 2H2O}n (5) (PDA = pyridine-2,6-dicarboxylic anion), was designed and synthesized under hydrothermal conditions. Complexes 1-3 (chainlike polymer, {[Pr(PDA)(HPDA)(H2O)2] x 4H2O}n (1) was also obtained independently by us, although it has been reported recently by Ghosh et al.) were fabricated successfully by simply tuning the Pr/PDA ratio and exhibited various and intriguing topological structures from a 1D chain to a 3D network. While the synthetic strategy of 5 was triggered and further performed only after 1 was structurally characterized. The complexes were characterized by X-ray single-crystal determination, spectroscopic, and variable-temperature magnetic susceptibility analyses. In complex 2 an unusual nanosized square motif as a building block constructed by eight Pr ions was further assembled into a highly ordered 2D grid compound. In complex 3 the decanuclear Pr metal-based structure as a repeat unit interpenetrated to form a novel 3D polymer. Complex 4 was a 3D network polymer fabricated through a hexanuclear Pr ring as a building block, and ClO4- anions as guests were trapped in the cavity. In complex 5 six Pr atoms, two SO4(2-) anions, and carboxylic oxygen bridges constructed an intriguing rectangle structure as a repeat unit in the grid to form a 2D coordination polymer in which the unique bi-bidentate coordination mode of SO4(2-) anion was observed.  相似文献   

7.
在水溶液中培养了甘氨酸镨、钕的针状晶体,元素分析结果表明可用Ln(Gly)3Cl3·3H2O表示(Ln为Pr,Nd;Gly为甘氨酸)。用X射线衍射方法测定了Pr(Gly)3Cl3·3H2O的单晶结构,其结构式为{[Pr(Gly)3·(H2O)2]·Cl3·H2O}n,属正交晶系,空间群P212121,每一晶胞中有4个络合单元,形成一维链式聚合物·晶胞参数如下:α=4.779(1)Å,b=12.052(3)Å,c=30.953(11)Å。络合单元中镨为九配位,其配位多面体为畸变的三冠三角棱柱体。  相似文献   

8.
The preparations and structures are described of four new polyoxostibonates, [Co(p-MeC(6)H(4)Sb)(12)O(28){Co(H(2)O)(3)}(4)]Cl(2)·6H(2)O, [Co(p-ClC(6)H(4)Sb)(12)O(28){Co(H(2)O)(3)}(4)]Cl(2)·22H(2)O, (PhCH(2)NMe(3))(2)[Zn(p-ClC(6)H(4)Sb)(12)O(28)Zn(4)Cl(2.54)Br(1.46)]·8MeCN·H(2)O and [BaCoH(4)(p-MeC(6)H(4)Sb)O(28)]·5H(2)O. Each of these has a framework of 12 (RSb) groups linked by 28 O atoms, with one transition metal ion in a tetrahedral site in the centre. Other metal ions are coordinated to the polyhedral faces. Three of the complexes have the ε Keggin ion geometry, while the fourth is a δ isomer.  相似文献   

9.
SbOSb bonds in (Ph3ClSb)2O and PH3SbO are cleaved readily by methanol and acetylacetone. The reactions provide convenient synthetic routes for Ph3Sb(OMe)Cl, Ph3Sb(OMe)2, Ph3Sb(acac)Cl, and Ph3Sb(acac)OH. Characterization of these compounds by infrared, Raman, and 1H NMR spectral measurements is reported.  相似文献   

10.
The novel dimeric compounds [Ph(2)Sb(O(2)PR(2))O](2).2CH(2)Cl(2) [R = cycl-C(6)H(11) (2) and cycl-C(8)H(15) (3)] have been synthesized by reacting diphenylantimony trichloride (1) with 3 mol equiv of silver acetate followed by 1 mol equiv of the phosphinic acid. By the same route under more stringent conditions to exclude moisture, the mixed phosphinate-acetate [Ph(2)Sb(O(2)P(C(6)H(11))(2))(O(2)CMe)](2)O (4) was isolated and characterized. Treatment of 2 with acetic acid/water affords the tetranuclear cage Ph(8)Sb(4)O(4)(OH)(2)(O(2)P(C(6)H(11))(2))(2).CH(3)COOH.CH(2)Cl(2) (5); it is possible to convert 5 to 2 by heating it with an excess of the phosphinic acid. Compounds 2, 3, and 5 have been characterized by X-ray structural analysis. All of them possess four membered Sb(2)O(2) rings with hexacoordinated antimony. In 5 the antimony atoms in the two Sb(2)O(2) rings are connected by oxo bridges on two sides to give an Sb(4)O(6) cage. These structures are correlated with those of known tin cages.  相似文献   

11.
The tungsten imido guanidinate and amidinate complexes W(NR)Cl(3)[R'NC(NMe(2))NR'] and W(NR)Cl(3)[R'NC(Me)NR'] (R = Ph, (i)Pr, Cy; R' = (i)Pr, (t)Bu, TMS) were synthesized by reacting the corresponding imido complex W(NR)Cl(4)(OEt(2)) with the appropriate lithium amidinate or guanidinate. Crystallographic structure determination of W(N(i)Pr)Cl(3)[(i)PrNC(NMe(2))N(i)Pr] and W(N(i)()Pr)Cl(3)[(i)PrNC(Me)N(i)Pr] allows comparison of structural features between the guanidinate and amidinate ligand in the presence of an identical ancillary ligand set.  相似文献   

12.
A new class of Mo/Fe/S clusters with the MoFe(3)S(3) core has been synthesized in attempts to model the FeMo-cofactor in nitrogenase. These clusters are obtained in reactions of the (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (I), (n)Pr (II)] clusters with CO. The new clusters include those preliminarily reported: (Cl(4)-cat)MoFe(3)S(3)(PEt(3))(2)(CO)(6) (III), (Cl(4)-cat)(O)MoFe(3)S(3)(PEt(3))(3)(CO)(5) (IV), (Cl(4)-cat)(Pyr)MoFe(3)S(3)(PEt(3))(2)(CO)(6) (VI), and (Cl(4)-cat)(Pyr)MoFe(3)S(3)(P(n)Pr(3))(3)(CO)(4) (VIII). In addition the new (Cl(4)-cat)(O)MoFe(3)S(3)(P(n)Pr(3))(3)(CO)(5) cluster (IVa), the (Cl(4)-cat)(O)MoFe(3)S(3)(PEt(3))(2)(CO)(6)cluster (V), the (Cl(4)-cat)(O)MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (Va), the (Cl(4)-cat)(Pyr)MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (VIa), and the (Cl(4)-cat)(P(n)Pr(3))MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (VII) also are reported. Clusters III-VIII have been structurally and spectroscopically characterized. EPR, zero-field (57)Fe-M?ssbauer spectroscopic characterizations, and magnetic susceptibility measurements have been used for a tentative assignment of the electronic and oxidation states of the MoFe(3)S(3) sulfur-voided cuboidal clusters. A structural comparison of the clusters with the MoFe(3)S(3) subunit of the FeMo-cofactor has led to the suggestion that the storage of reducing equivalents into M-M bonds, and their use in the reduction of substrates, may occur with the FeMo-cofactor, which also appears to have M-M bonding. On the basis of this argument, a possible N(2)-binding and reduction mechanism on the FeMoco-cofactor is proposed.  相似文献   

13.
The reaction of [Ti(NR)Cl(2)(py)(3)](R = (t)Bu, p-tolyl, 2,6-C(6)H(3)(i)Pr(2)) with [{Li(bdmpza)(H(2)O)}(4)][bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate] and [{Li(bdmpzdta)(H(2)O)}(4)][bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate] affords the corresponding complexes [Ti(NR)Cl(kappa(3)-bdmpzx)(py)](x = a, R = (t)Bu 1, p-tolyl 2, 2,6-C(6)H(3)(i)Pr(2) 3; x = dta, R =(t)Bu 4, p-tolyl , 2,6-C(6)H(3)(i)Pr(2) 6), which are the first examples of imido Group 4 complexes stabilized by heteroscorpionate ligands. The solid-state X-ray crystal structure of 1 has been determined. The titanium centre is six-coordinate with three fac-sites occupied by the heteroscorpionate ligand and the remainder of the coordination sphere being completed by chloride, imido and pyridine ligands. The complexes are 1-6 fluxional at room temperature. The pyridine ortho- and meta-proton resonances show evidence of dynamic behaviour for this ligand and variable-temperature NMR studies were carried out in order to study their dynamic behaviour in solution. The complexes [Nb(NR)Cl(3)(py)(2)](R = (t)Bu, p-tolyl, 2,6-C(6)H(3)(i)Pr(2)) reacted with [{Li(bdmpza)(H(2)O)}(4)] and (Hbdmpze)[bdmpze = 2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide], the latter with prior addition of (n)BuLi, to give the complexes [Nb(NR)Cl(2)(kappa(3)-bdmpzx)](x = a, R =(t)Bu 7, p-tolyl 8, 2,6-C(6)H(3)(i)Pr(2) 9; x = e, R = (t)Bu 10, p-tolyl 11, 2,6-C(6)H(3)(i)Pr(2)) 12 and these are the first examples of imido Group 5 complexes with heteroscorpionate ligands. The structures of these complexes have been determined by spectroscopic methods.  相似文献   

14.
Initial attempts to prepare new Ln-Cd-Te-O-Cl compounds led to the isolation of two novel cadmium tellurium(IV) oxychlorides with two different types of structures, namely, [Cd(2)(Te(6)O(13))][Cd(2)Cl(6)] and Cd(7)Cl(8)(Te(7)O(17)). Both compounds feature novel polymeric tellurium(IV) oxide anions and unusual cadmium chloride substructures. The structure of [Cd(2)(Te(6)O(13))][Cd(2)Cl(6)] is composed of 1D [Cd(2)Cl(6)](2)(-) double chains and (002) [Cd(2)(Te(6)O(13))](2+) layers. The 1D Te(6)O(13)(2)(-) slab of the [Cd(2)(Te(6)O(13))](2+) layer is formed by TeO(3), TeO(4), and TeO(5) groups via corner- and edge-sharing, and it contains six- and seven-membered tellurium(IV) polyhedral rings. The structure of Cd(7)Cl(8)(Te(7)O(17)) features a 3D network with long-narrow tunnels along the b axis. The two types of structural building blocks are 1D [Te(7)O(17)](6)(-) anions and unusual corrugated [Cd(7)Cl(8)](6+) layers based on "cyclohexane-like" Cd(3)Cl(3) rings.  相似文献   

15.
The 3-amino-1,2,4-triazole (atz)-based manganese complex was prepared and characterized through single-crystal X-ray diffraction, IR, EPR, and UV–visible spectroscopy. In the crystal structure, individual complex are interconnected through N(O)–H…Cl hydrogen bonds into 1D undulating chains running parallel to the [110] direction of the unit cell. Chains further grow into 2D supramolecular layers by way of the lattice water molecules of coordination and the chloride anions (O–H…Cl). Layers pack along the b-axis of the unit cell mediated by O–H…Cl(N) and N–H…O(Cl) hydrogen bonds forming a 3D supramolecular architecture. The theoretical calculations were also performed to optimize the structure of the complexes in the gas phase to confirm the structures proposed by X-ray crystallography. In addition, IR and UV–visible spectra of complex were calculated and compared with the corresponding experimental spectra to complete the experimental structural identification. The three-dimensional Hirshfeld surface (3D-HS) and their relative two-dimensional fingerprint plots (2D-FP) reveal that the structure is dominated by H…Cl/Cl…H (50.5%), H…O/O…H (11.3%) and N…O/O…N (10.2%) contacts.  相似文献   

16.
用常规合成方法制备了基于Anderson结构阴离子的二维层状化合物[(C6H5NO2)2Pr(H2O)4](CrMo6O24H6)·2.5H2O,通过红外光谱和X射线单晶衍射对其进行了表征.结果表明,该化合物属于单斜晶系,C2/c空间群.a=2.3442(9)nm,b=1.3291(5)nm,c=2.458(1)nm,β=103.08(1)°,V=7.460(5)nm3,R1=0.0727,wR2=0.1903.结构分析表明,[CrMo6O24H6]3-阴离子通过端氧担载一个配位的Pr3+离子形成中性的(C6H5NO2)Pr(H2O)4(CrMo6O24H6)基团,相邻的中性基团在Ot—Pr—Ot桥联下形成一维链,链与链又通过异烟酸的桥联形成二维层状结构.  相似文献   

17.
Ce(NO3)3.6H2O or Pr(NO3)3.6H2O and pyridine-2,6-dicarboxylic acid form a linear coordination polymeric structure under hydrothermal conditions. Hexameric water clusters join these linear chains through bonding to the metal ions. Other coordinated water and the carboxylate oxygen form an intricate array of hydrogen bonding resulting in a 3D network where each metal ion shows 9-coordination with an approximate D3 symmetry. Dimeric water clusters are also located in the void spaces. In the structure containing Pr(III), the water dimers are hydrogen-bonded to the hexamers, whereas in the Ce(III) structure, the dimers and the hexamers are far apart.  相似文献   

18.
卢江  梁晖  黎宝恩  张伟 《高分子学报》2001,31(3):357-360
在 - 40℃下 ,CH2 Cl2 中以α 氯代乙苯为引发剂 ,Ti(OiPr) 4 TiCl4复合物 (摩尔比为 1 3)为Lewis酸活化剂、nBu4NCl存在下先进行 β 蒎烯的活性聚合 ,30min后当单体转化率接近 10 0 %时 ,加入苯乙烯引发其活性聚合 .在苯乙烯低转化率 (15 %左右 )下终止反应 ,得到由 3~ 5个苯乙烯链节封端带苄氯端基的聚 β 蒎烯大分子引发剂 .1 H NMR分析表明每个大分子引发剂所带的苄氯端基数接近 1(1 1) .大分子引发剂与Ti(OiPr) 4 TiCl4复合后 ,CH2 Cl2 中 - 40℃下能顺利引发苯乙烯阳离子聚合 ,获得 β 蒎烯 苯乙烯嵌段共聚物 ;与氯化亚铜(CuCl) 2 ,2′ 联二吡啶 (bipy)复合 ,组成原子转移自由基聚合 (ATRP)引发体系 ,在甲苯中 110℃引发甲基丙烯酸甲酯 (MMA)自由基聚合 ,得到 β 蒎烯 MMA嵌段共聚物 ,但此时大分子引发剂的引发效率小于 10 0 %  相似文献   

19.
The easy synthesis of [Sb2W20O70{Ru(p-cymene)}2](10-) by the reaction between the organometallic precursor [Ru(p-cymene)Cl2]2 and [Sb2W20O70]14-, formed in situ, confirms the importance of the organometallic route to well defined ruthenium(+II)-substituted heteropolytungstates.  相似文献   

20.
Xu N  Shi W  Liao DZ  Yan SP  Cheng P 《Inorganic chemistry》2008,47(19):8748-8756
Lanthanide coordination polymers were synthesized from Pr(III), Nd(III), and Gd(III) salts; 2-hydroxynicotinic acid (Hnica); and MnSO 4.H 2O under hydrothermal conditions. In the absence of (CH 3) 3CCOONa, 1D polymers with an infinite Ln(III)-O-Ln(III) chain structure, [Pr(Hnica)(H 2O) 2SO 4] n ( 1), [Nd(Hnica)(H 2O) 2SO 4] n ( 2), and [Gd(Hnica)(H 2O) 2SO 4] n ( 3), were generated. When (CH 3) 3CCOONa was added to the synthetic systems, 2D coordination polymers {[Pr 3(Hnica) 6(H 2O) 9].3H 2O.SO 4.NO 3} n ( 4), {[Nd 3(Hnica) 6(H 2O) 9].3H 2O.SO 4.NO 3} n ( 5), and {[Gd(Hnica) 2(H 2O) 2]ClO 4.H 2O} n ( 6) were obtained. Complexes 4 and 5 both exhibit Kagome lattice structure, while 6 displays a rhombic grid structure. All complexes were characterized by elemental analysis, IR spectra, UV-vis spectra, and X-ray single-crystal diffraction. The variable-temperature magnetic susceptibility studies reveal ferromagnetic interactions between gadolinium(III) ions in 3 and 6 and antiferromagnetic interactions in 1, 2, 4, and 5.  相似文献   

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