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1.
在溶剂热条件下,以不对称三羧酸5-(6-羧酸-2-萘基)-间苯二羧酸(H3L)为配体合成了2个镉的金属-有机骨架化合物:{[Cd3L2(H2O)3]·6DMF}n(1)和{[Cd3L2(H2O)4]·3DMA}n(2)。通过X射线单晶衍射,粉末衍射,热重和红外光谱进行了结构表征。结构分析表明,1和2形成3,6-连接的三维结构,其拓扑符号分别为:(45.64.86)(432和(612.83)(632。此外,还对2个化合物进行了荧光分析。  相似文献   

2.
氢氧化钠与己二胺四甲叉膦酸(H8L)在水溶液中反应合成了一个新型的配合物[Na3(H6L)2(H2O)8][Na(H2O)6]·8H2O(1),其结构经IR和X-射线单晶衍射表征。结果表明1属P-1空间群,晶胞参数a=7.705 9(1) , b=11.655 6(2) , c=18.119 7(3) ,α=97.247(1)°,β=94.797(1)°, γ=101.827(1)°。 1中部分钠离子通过与四膦酸配体中的氧原子配位,形成一维链状结构{[Na3(H6L)2(H2O)8]-},该阴离子链的电荷被孤立离子团[Na(H2O)6]+平衡。在未配位的膦酸基团、氨基、配位水分子、结晶水分子之间的氢键相互作用下,化合物堆积形成一个结构致密的三维超分子结构。  相似文献   

3.
在乙酸钠水溶液中, 采用微波加热一步自组装策略合成了一系列罕见的2,6-吡啶二羧酸修饰的稀土嵌入Keggin型碲钨酸盐(PTEA)7H3K[RE2(B-α-TeW9O33)3W3O5(H2O)3(HDPA)]·22H2O[RE=Ce3+(1), Pr3+(2), Nd3+(3), Sm3+(4); H2DPA=2,6-吡啶二羧酸; PTEA=质子化的三乙醇胺]. 化合物1~4的聚阴离子由3个三缺位Keggin型 [B-α-TeW9O33]8-构筑块通过1个{RE2W3O5(H2O)3(HDPA)}13+异金属簇连接而成. 该异金属簇中, 2,6-吡啶二羧酸作为四齿配体与2个稀土离子(RE1和RE2)配位形成平面三杂环结构, 且RE1和RE2所在平面与W2, W2A, W16形成的平面互相垂直. 此外, 化合物1可与羧基化多壁碳纳米管(CMWCNT)复合形成1-CMWCNT复合材料. 该复合材料可以作为电极材料构建电化学生物传感器, 用于检测特定的DNA序列.  相似文献   

4.
水热条件下,合成了一个三维配位聚合物[Ni2(BDC)2(m-bix)(H2O)3·3H2O]n(1)[BDC=对苯二甲酸,m-bix=1,3-双(咪唑基-1-甲基)-苯],并通过红外,热重和X-射线单晶衍射进行了表征。X射线衍射结果表明化合物含有类似配位环境的金属2个Ni2+离子,2个BDC2-配体,1个m-bix分子,3个配位水分子和3个游离的溶剂水分子。两个Ni2+离子分别采用八面体构型,通过桥联水分子形成双核单元,然后通过全部脱质子的BDC形成三维孔洞结构,m-bix配体通过连接两类双核金属原子形成三维框架,游离水分子存在于框架之中。有趣的是,化合物的结构是单一六节点,具有自穿插特征。而且对化合物的红外和热重性质进行了表征。  相似文献   

5.
随着智能材料的不断发展,多重刺激响应型紫精配位聚合物有望应用于材料学和生物学等工程领域,引起了广泛的兴趣。为了获得此类化合物,以羧苄基紫精、1,1’-双(4-羧苄基)-4,4’-联吡啶二氯化物(H2BpybcCl2)为功能配体,与过渡金属离子Ni2+(1)、Mn2+(2)和Co2+(3)自组装反应,形成3个相同结构的二维配位聚合物{[M2(Bpybc)3(H2O)6]·(OH)4·nH2O}n。由于紫精自由基的存在,在紫外灯照射下,3个化合物均表现出明显的光致变色行为。加热的条件下,3个化合物也表现出由于脱水导致的配位场d-d跃迁而发生的颜色变化。  相似文献   

6.
关磊  刘泽汉  任冰洁 《合成化学》2019,27(11):904-908
以4,5-二羟基苯-1,3-二磺酸钠(Na2H2L)和4,4′-bipy为原料,采用水热法与Co(NO3)2反应合成了新的含氮配体钴配合物[Co(4,4′-bipy)(H2O)4]·H2L·2H2O(1)(H2L2-=4,5-二羟基苯-1,3-二磺酸根离子,4,4′-bipy=4,4′-联吡啶),其结构和组成经X-射线单晶衍射、红外光谱、元素分析和热重分析表征。晶体结构解析表明:钴离子与4,4′-bipy和水分子配位,形成扭曲的八面体配位构型。H2L2-配体没有配位,仅起平衡电荷作用。在结构单元中,[Co(4,4′-bipy)(H2O)4]2+, H2L2-和自由水分子之间通过氢键相连。配合物的荧光发射峰与配体相比发生了蓝移,最大发射峰位于357 nm。  相似文献   

7.
合成了9种N,O-配体化合物L1~L9.化合物L1~L4分别与0.5 equiv.Co2(CO)8发生氧化还原配位反应生成中性单核钴化合物1~4;L5~L7分别与1 equiv.Co2(CO)8发生歧化和氧化还原配位反应;L8与5/6 equiv.Co2(CO)8以及1.2equiv.MeOH和0.4 equiv.H2O发生歧化和氧化还原配位反应;L9与0.5 equiv.Co2(CO)8发生歧化配位反应生成同钴核离子对化合物5~9.这些化合物中的阴离子均为[Co(CO)4]-.相应地,化合物8中的阳离子是三核钴簇,其它化合物中的阳离子都是单核钴.化合物1~9通过FT-IR谱...  相似文献   

8.
以苯并咪唑(HL1)和3,6 二氯哒嗪在钠催化下反应制得配体3-氯-6-(苯并咪唑-1-基)哒嗪(L2);采用溶液法和水热法,L1分别与含有银、铜过渡金属盐反应合成了3种新的有机金属苯并咪唑配合物[AgL1n(1),[Cu4(HL1)4(O)(Cl)6](2)和{[Cu(HL1)2]·SiF6}(3);采用溶液法,L2与Zn(NO3)2·6H2O经配位反应合成了配合物{[Zn(L2)3(NO3)]NO3}(4),其结构经IR,元素分析和X-射线单晶衍射表征。结果表明:1通过苯并咪唑桥连形成一维链状结构,2由苯并咪唑和氯离子桥接形成四核结构,3和4均显示一个单核结构,3的金属中心原子采用二配位构型,4的金属中心原子采用四配位构型。此外,研究了配体HL1与1,及配体L2与4的荧光性能。结果表明:与HL1相比,1的最大发射波长发生了红移;而4相对于配体L2其最大发射峰发生明显蓝移。  相似文献   

9.
陈钦  郭依洁  张冲  张淑华 《合成化学》2020,28(10):869-874
利用水热法合成了4-(N,N′-双(4-羧基苄基)氨基)苯磺酸(H3L)的两个离子型配合物:[Mn(phen)2(H2O)2]?(HL)?(H2O)4(1)和[Zn(phen)2(H2O)2]?(HL)?(H2O)6(2, phen =邻菲罗啉),其结构经FL、 IR、元素分析、X-射线单晶衍射、 X-射线粉末衍射和TG表征。结果表明:化合物1属于单斜晶体,P21/c空间群,晶胞参数a=11.997(1) Å, b=22.978(1) Å, c=18.093(1) Å, β=92.749(3)°, V=4981.8(3) Å3, Z=4。化合物2属于单斜晶体,P21/c空间群,晶胞参数a=11.861(1) Å, b=22.816(1) Å, c=18.251(1) Å, β=92.832(5)°, V=4932.8(5) Å3,Z=4。化合物2有较好的荧光性质;初始分解温度为80 ℃。   相似文献   

10.
在水热条件下,Cu(Ⅱ)-H2biim配合物与Dawson型钨磷酸盐构筑了1个无机-有机杂化化合物[Cu(H2biim)2(H2O)][{Cu(H2biim)2}2(P2W18O62)]·11H2O(1)(H2biim=2,2'-联咪唑)。 通过单晶X射线衍射、红外光谱(IR)、X射线粉末衍射(XRD)、元素分析、电化学分析等技术手段对其进行了表征。 结构分析表明,在化合物1分子中,[P2W18O62]6-单元作为双齿配体与2个Cu2+离子配位形成双支撑的杂多阴离子[{Cu(H2biim)2}2(P2W18O62)]2-,在其外部有1个游离的[Cu(H2biim)2(H2O)]2+ 和11个H2O分子。 H2biim分子与杂多阴离子/H2O分子间存在氢键,通过氢键、静电和π-π堆积作用,进一步构成具有3D结构的晶体材料。 该晶体化合物对H2O2和NaNO2的还原具有良好的电催化作用;同时,作为酸催化剂用于合成环己酮乙二醇缩酮反应,催化活性高,可重复使用。  相似文献   

11.
Song JL  Lei C  Mao JG 《Inorganic chemistry》2004,43(18):5630-5634
Hydrothermal reactions of lanthanide metal salts with MeN(CH(2)CO(2)H)(CH(2)PO(3)H(2)) (H(3)L) and 5-sulfoisophthalic acid monosodium salt (NaH(2)BTS) lead to four isomorphous lanthanide carboxylate-phosphonate-sulfonate hybrids, namely, Ln(H(2)L)(HBTS)(H(2)O)(2).H(2)O (Ln = La (1), Pr (2), Nd (3), Gd (4)). Their structures have been established by X-ray single-crystal diffraction. The interconnection of the lanthanide(III) ions by carboxylate-phosphonate ligands results in a 1D double chain; these double chains are further bridged by bidentate bridging carboxylate-sulfonate ligands to form a <011> layer. The luminescent properties of compounds 3 and 4 have also been studied.  相似文献   

12.
Du ZY  Xu HB  Mao JG 《Inorganic chemistry》2006,45(24):9780-9788
Hydrothermal reactions of lanthanide(III) salts with m-sulfophenylphosphonic acid (H3L1) and 1,10-phenanthroline (phen) or N,N'-piperazinebis(methylenephosphonic acid) (H4L2) afforded six novel lanthanide(III) sulfonate-phosphonates based on tetranuclear clusters, namely, [La(2)(L1)2(phen)4(H2O)].4.5H2O (1), [Ln2(L1)2(phen)2(H2O)5].3H2O (Ln = Nd, 2; Eu, 3; Er, 4), and [Ln2(HL1)(H2L2)2(H2O)4].8H2O (Ln = La, 5; Nd, 6). Compounds 2-4 contain discrete tetranuclear lanthanide(III) cluster units in which four lanthanide(III) ions are bridged by two tridentate and two tetradentate phosphonate groups. In compound 1, the tetranuclear clusters are further interconnected into a 1D chain through the coordination of the sulfonate groups. The structures of compounds 5 and 6 can be viewed as a 3D architecture based on a different types of tetranuclear cluster units that are interconnected by bridging H2L2 anions. In the tetranuclear clusters of compounds 5 and 6, the four lanthanide(III) centers are interconnected by only two HL1 ligands. Compound 2 is a luminescent material in the near-IR region, whereas compound 3 displays a strong luminescent emission band in the red-light region. Magnetic property measurements of compounds 2-4 and 6 indicate that there are strong antiferromagetic interactions between magnetic centers within the cluster units.  相似文献   

13.
The first examples of lanthanide(III) organoarsonates, Ln(L(1))(H(2)O)(3) (Ln = La (1), H(3)L(1) = 4-hydroxy-3-nitrophenylarsonic acid), Ln(L(1))(H(2)O)(2) (Ln = Nd (2), Gd (3)), and mixed-ligand lanthanide(III) organoarsonates, Ln(2)(HL(1))(2)(C(2)O(4))(H(2)O)(2) (Ln = Nd (4), Sm (5), Eu (6)), were hydrothermally synthesized and structurally characterized. Compounds 1-3 feature a corrugated lanthanide arsonate layer, in which 1D lanthanide arsonate inorganic chains are further interconnected via bridging L(1)(3-) ligands. Compounds 4-6 exhibit a complicated 3D network. The interconnection of the lanthanide(III) ions by the bridging arsonate ligand leads to the formation of a novel 3D framework with long narrow 1D tunnels along the a-axis, with the oxalate anions are located at the above tunnels and bridging with lanthanide(III) ions. Compounds 2 and 4 exhibit the characteristic emission bands of the Nd(III) ion, whereas compound 6 displays the characteristic emission bands of the Eu(III) ion. The magnetic properties of compounds 3-6 were also investigated.  相似文献   

14.
Han F  Teng Q  Zhang Y  Wang Y  Shen Q 《Inorganic chemistry》2011,50(6):2634-2643
The monoamido lanthanide complexes stabilized by Schiff base ligand L(2)LnN(TMS)(2) (L = 3,5-Bu(t)(2)-2-(O)-C(6)H(2)CH═N-8-C(9)H(6)N, Ln = Yb (1), Y (2), Eu (3), Nd (4), and La (5)) were synthesized in good yields by the reactions of Ln[N(TMS)(2)](3) with 1.8 equiv of HL in hexane at room temperature. It was found that the stability of 1-5 depends greatly on the size of the lanthanide metals with the increasing trend of Yb ≈ Y < Nd < La. The amine elimination of Ln[N(TMS)(2)](3) with the bulky bidentate Schiff base HL' (L' = 3,5-Bu(t)(2)-2-(O)-C(6)H(2)CH═N-2,6-Pr(i)(2)-C(6)H(3)) afforded the monoamido lanthanide complexes L'(2)LnN(TMS)(2) (Ln = Yb (9), Y (10), Nd (11), and La (12)). While the amine elimination with the less bulky Schiff base HL' (L' = 3,5-Bu(t)(2)-2-(O)-C(6)H(2)CH═N-2,6-Me(2)-C(6)H(3)) yielded the desired monoamido complexes with the small metals of Y and Yb, L'(2)LnN(TMS)(2) (Ln = Yb (13) and Y (14)), and the more stable tris-Schiff base complexes with the large metals of La and Nd, yielded L'(3)Ln as the only product. Complexes 1-14 were fully characterized including X-ray crystal structural analysis. Complexes 1-5, 10, and 14 can serve as the efficient catalysts for addition of amines to carbodiimides, and the catalytic activity is greatly affected by the lanthanide metals with the active sequence of Yb < Y < Eu ≈ Nd ≈ La.  相似文献   

15.
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   

16.
Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2?:?3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.  相似文献   

17.
Heteropolynuclear organometallic compounds have been constructed by using two kinds of ferrocene-based ligands, 1,1'-ferrocenedicarboxylic acid (H(2)L(1)) and ferrocenecarboxylic acid (HL(2)). Reactions the ligand H(2)L(1) with copper(II) and nickel(II) salts, in the presence of pyridine, give a tetranuclear Cu(2)Fe(2) mixed-metallic box Cu(2)L(1)(2)(Py)(2)(DMF)(2)(H(2)O)(2) (1) and a tetranuclear heterobimetallic helix Ni(2)L(1)(2)(Py)(4)(H(2)O) (2), respectively. In these complexes, the ferrocene moieties show cisoid conformations which lead to the formation of the finite coordination geometry, i.e. to molecular complexes. Interactions of the ligand H(2)L(1) with lanthanide ions afford two-dimensional networks [La(2)L(1)(3)(CH(3)OH)(4)]( infinity ) (3), [Eu(2)L(1)(3)(H(2)O)(5)]( infinity ) (4), and [Gd(2)L(1)(3)(CH(3)OH)(2)(H(2)O)(3)]( infinity ) (5), respectively, in which transoid conformations of the ferrocene moiety provide opportunities to form infinite 2-D networks. It is suggested that the conformational freedom of the ferrocene moiety makes the ligand L(1) display different conformations and coordination modes in these complexes. In addition, the pi.pi interactions related to the ferrocene moieties were also found to stabilize the supramolecular architectures in the solid state. As a comparison, reaction of lanthanide ions with the ligand HL(2) resulted in three isostructural heterodinuclear windmill-shaped compounds Ln(2)L(2)(6)(CH(3)OH)(2)(H(2)O)(5) [Ln = La (6), Eu (7), and Gd (8)] by simply diffusing the solutions of lanthanide ions into the mixture of HL(2) and NaOH, respectively. Electrochemical properties of the ferrocene-containing complexes 1-8 are also investigated in the solution or solid state.  相似文献   

18.
钱长涛  王兵  邓道利 《有机化学》1994,14(3):265-269
本文通过双(2-甲氧乙基环戊二烯基)稀土氯化物与环戊二烯基钠在室温下反应, 经升华得新配合物,(CH~3OCH~2CH~2C~5H~4)~2Ln(C~5H~5) (Ln=La,Pr,Nd), 这些配合物都经红外、光电子能谱、质谱、核磁共振谱和元素分析鉴定;并且比较了具有不同配位环境的三茂稀土配合物-氢化钠体系还原1-己烯的活性。  相似文献   

19.
Hydrothermal reactions of the lanthanide chlorides with MeN(CH2CO2H)(CH2PO3H2), (H3L1) (or Me2NCH2PO3H2, H2L2) and sodium oxalate lead to seven new lanthanide oxalate phosphonate hybrids with three types of 3D network structures, namely, [Ln(C2O4){MeNH(CH2CO2)(CH2PO3H)}]0.5 H2O (Ln=Nd: 1; Eu: 2; Gd: 3), [Ln4(C2O4)5(Me2NHCH2PO3)2(H2O)4]2 H2O (Ln=La: 4, Nd: 5), [Ln3(C2O4)4(Me2NHCH2PO3)(H2O)6]6 H2O (Gd: 6, Er: 7). Their structures have been established by X-ray single-crystal diffraction. Complexes 1-3 are isostructural and feature a 3D network formed by the interconnection of 3D network of {Ln(H2L1)}2+ with 1D chains of {Ln(C2O4)}+. Complexes 4 and 5 are isostructural and feature a complex 3D network built from 3D network of lanthanide oxalate and {Ln4(HL2)2} units. The isostructural 6 and 7 form another type of 3D network composed of porous lanthanide-oxalate network inserted by 1D chains of lanthanide-oxalate phosphonate. Compounds 1, 5 and 7 are luminescent materials in the near IR region. Compounds 3 and 6 exhibit a broad blue fluorescent emission band at 451 and 467 nm, respectively. Compound 2 displays very strong and sharp emission bands at 592, 616 and 699 nm with a long luminescent lifetime of 1.13 ms.  相似文献   

20.
在非水体系中首次合成了硝酸稀土(III)的邻香兰素(2-羟基-3-甲氧基苯甲醛)与乙二胺(L^1)、联苯胺(L^2)、邻苯二胺(L^3)和间苯二胺(L^4)的双Schiff碱配合物(1-8)。通过测定红外光谱、摩尔电导、X射线衍射和X射线光电子能谱推断了配合物的结构和键合情况,配合物的中心金属离子与配体中的二个氮原子、二个氧原子和二个硝酸根中的四个氧原子配位,其配位数为8。通过热重及差热分析发现配合物在低于230℃时很稳定,对于同一配体与不同中心金属离子形成的配合物来说,其热稳定性随稀土离子半径的减小而降低。在77K时测试了铕配合物的激发光谱和荧光光谱,观察到Eu^3^+的特征发射峰。  相似文献   

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