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1.
采用芳香族π共轭及含氮原子有机连接剂,合成同构铽、铕发光配位聚合物(CPs){[Eu(PLIA)1.5(H2O)2]·H2O}n (1)和{[Tb(PLIA)1.5(H2O)2]·H2O}n (2),其中H2PLIA=5-((吡啶-4-基甲基)氧基)苯-1,3-二甲酸。对合成的配合物进行了结构测定、表征和荧光痕量识别实验研究。2个同构配合物具有理想的三维框架结构,ππ堆积及氢键等弱相互作用增强了其化学稳定性;表征显示配位聚合物12具有良好的荧光性质、结晶性、热力学稳定性及结构完整性,可作为荧光传感的材料。12对水溶液中的Zr4+、Cr2O72-和Fe3+、HPO42-具有选择性好、灵敏度高的荧光识别能力,其检出限分别为0.139 μmol·L-1(1,Zr4+)、0.626 μmol·L-1(1,Cr2O72-)、0.430 μmol·L-1(2,Fe3+)、1.36 μmol·L-1(2,HPO42-)。探究了12作为探针的荧光猝灭机理。更有趣的是,12具有指纹识别性能,其荧光指纹纹路清晰连贯,细节明显,可被清晰观察。  相似文献   

2.
采用溶剂热法,以含氮四羧酸3,5-二(3'',5''-二羧苯)-1H-1,2,4-三唑(H4BDT)为配体,成功合成了4种同构镧系金属有机框架(Ln-MOFs):{[La3(BDT)2(HCOO)(H2O)5]·0.5H2O·3DMF}n(1)、{[Ce3(BDT)2(HCOO)(H2O)5]·3DMF}n(2)、{[Pr3(BDT)2(HCOO)(H2O)5]·3DMF}n(3)和{[Nd3(BDT)2(HCOO)(H2O)5]·3DMF}n(4),并采用单晶X射线衍射、粉末X射线衍射、元素分析、热重、傅里叶换红外光谱、N2吸附实验和荧光光谱对其进行表征。结果表明,这些Ln-MOFs均为单斜C2/m空间群晶体,是双核为无机建筑单元的三维介孔结构。其中2可选择性荧光检测Fe3+离子和盐酸环丙沙星药物分子,检测限分别为4.59和0.77 μmol·L-1。  相似文献   

3.
在溶剂热条件下,成功合成了一种稳定的配位聚合物[Cd2(L)(bpb)(H2O)4]·0.5H4L(1)(H4L=1,1''-乙烷基联苯-3,3'',5,5''-四羧酸,bpb=1,4-二(4-吡啶基)苯)。1在不同的有机溶剂和水中表现出优异的稳定性。1可通过荧光猝灭检测水中的罗红霉素(ROX)和B4O72-,检测限分别为0.21和1.59μmol·L-11可成功用于延河水中ROX和B4O72-的测定。此外,分析讨论了其传感机理。  相似文献   

4.
在溶剂热条件下,成功合成了一种稳定的配位聚合物[Cd2(L)(bpb)(H2O)4]·0.5H4L (1)(H4L=1,1''-乙烷基联苯-3,3'',5,5''-四羧酸,bpb=1,4-二(4-吡啶基)苯)。1在不同的有机溶剂和水中表现出优异的稳定性。1可通过荧光猝灭检测水中的罗红霉素(ROX)和B4O72-,检测限分别为0.21和1.59 μmol·L-11可成功用于延河水中ROX和B4O72-的测定。此外,分析讨论了其传感机理。  相似文献   

5.
采用溶剂热法,以含氮四羧酸3,5-二(3′,5′-二羧苯)-1H-1,2,4-三唑(H4BDT)为配体,成功合成了4种同构镧系金属有机框架(Ln-MOFs):{[La3(BDT)2(HCOO)(H2O)5]·0.5H2O·3DMF}n (1)、{[Ce3(BDT)2(HCOO)(H2O)5]·3DMF}n (2)、{[Pr3(BDT)2(HCOO)(H2O)5]·3DMF}n (3)和{[Nd3(BDT)2(HCOO)(H2O)5]·3DMF}n (4),并采用单晶X射线衍射、粉末X射线衍射、元素分析、热重、红外、N2吸附实验和荧光光谱对其进行表征。结果表明,这些Ln-MOFs均为单斜C2/m空间群晶体,是双核为无机建筑单元的三维介孔结构。其中2可选择性荧光检测Fe3+离子和盐酸环丙沙星药物分子,检测限分别为4.59和0.77 μmol·L-1。  相似文献   

6.
采用芳香族π共轭及含氮原子有机连接剂,合成同构铽、铕发光配位聚合物(CPs){[Eu (PLIA)1.5(H2O)2]·H2O}n (1)和{[Tb (PLIA)1.5(H2O)2]·H2O}n (2),其中H2PLIA=5-((吡啶-4-基甲基)氧基)苯-1,3-二甲酸。对合成的配合物进行了结构测定、表征和荧光痕量识别实验研究。2个同构配合物具有理想的三维框架结构,ππ堆积及氢键等弱相互作用增强了其化学稳定性;表征显示配位聚合物12具有良好的荧光性质、结晶性、热力学稳定性及结构完整性,可作为荧光传感的材料。12对水溶液中的Zr4+、Cr2O72-和Fe3+、HPO42-具有选择性好、灵敏度高的荧光识别能力,其检出限分别为0.139 μmol·L-1(1,Zr4+)、0.626 μmol·L-1(1,Cr2O72-)、0.430 μmol·L-1(2,Fe3+)、1.36 μmol·L-1(2,HPO42-)。探究了12作为探针的荧光猝灭机理。更有趣的是,12具有指纹识别性能,其荧光指纹纹路清晰连贯,细节明显,可被清晰观察。  相似文献   

7.
采用溶剂热法合成了一种新型的钴(Ⅱ)基配合物,即{[Co(Hppc)2][Co2(4,4''-bipy)(H2O)4](SO4)2·2H2O}n (1),其中H2ppc=5-(3-吡啶基)-1H-吡唑-3-羧酸,4,4''-bipy=4,4''-联吡啶。配体H2ppc是由吡啶环、吡唑环和羧基共同组成,同时兼具了刚性和柔性。通过单晶X射线衍射对配合物1进行了结构测定。结果显示所合成的配合物1结晶在单斜晶系C2/c空间群,包括2个晶体学独立部分:二维层状[Co(Hppc)2]和一维链状[Co2(4,4''-bipy)(H2O)4]2-,并形成具有{44·62}{4}2拓扑网络结构的共晶化合物。此外,配合物1呈现出良好的电化学发光(ECL)性能以及良好的超级电容器性能。  相似文献   

8.
徐涵  潘兆瑞  亓昭鹏  孙洁 《无机化学学报》2022,38(12):2479-2490
在溶剂热条件下,合成了3个基于V型配体的Zn(Ⅱ)金属有机骨架:{[Zn2(BIDPS)2(OBA)2]·DMA}n(1)、{[Zn (BIDPT)(PA)]·DMF}n(2)和{[Zn (BIDPS)(PA)(H2O)2]·2H2O}n(3)(BIDPS=4,4''-二(1-咪唑基)苯砜,H2OBA=4,4''-二苯醚二甲酸,H2PA=帕莫酸,BIDPT=4,4''-二(1-咪唑基)苯硫醚)。利用X射线单晶衍射、红外光谱、元素分析、热重分析、X射线粉末衍射对其结构进行了表征。配合物1具有二重穿插的三维cds拓扑网络结构。配合物2为二维(4,4)层状结构,层与层之间通过互锁形成2D→3D的三维金属有机骨架。配合物3具有一维链状结构,一维链通过分子内和分子间氢键连接,形成三维超分子结构。荧光研究表明,配合物1~3可以在pH=4~10的水溶液中稳定存在,且在水中具有较强的发光性能,可作为检测2,4,6-三硝基苯酚和Fe3+的发光传感器,具有较高的灵敏度和选择性。  相似文献   

9.
在溶剂热条件下,合成了3个基于V型配体的Zn(Ⅱ)金属有机骨架:{[Zn2(BIDPS)2(OBA)2]·DMA}n(1)、{[Zn(BIDPT)(PA)]·DMF}n(2)和{[Zn(BIDPS)(PA)(H2O)2]·2H2O}n(3)(BIDPS=4,4''-二(1-咪唑基)苯砜,H2OBA=4,4''-二苯醚二甲酸,H2PA=帕莫酸,BIDPT=4,4''-二(1-咪唑基)苯硫醚)。利用X射线单晶衍射、红外光谱、元素分析、热重分析、X射线粉末衍射对其结构进行了表征。配合物1具有二重穿插的三维cds拓扑网络结构。配合物2为二维(4,4)层状结构,层与层之间通过互锁形成2D→3D的三维金属有机骨架。配合物3具有一维链状结构,一维链通过分子内和分子间氢键连接,形成三维超分子结构。荧光研究表明,配合物1~3可以在pH=4~10的水溶液中稳定存在,且在水中具有较强的发光性能,可作为检测2,4,6-三硝基苯酚和Fe3+的发光传感器,具有较高的灵敏度和选择性。  相似文献   

10.
利用六亚甲基四胺分别与苯氧乙酸、Cu(NO3)2·3H2O及2,4-二氯苯氧乙酸、Zn(NO3)2·6H2O反应,得到了2个新的一维配位聚合物,{[Cu2(pa)4](μ2-hmt)}n(1)和{{{[Zn3(dcpa)4(OH)]2(μ2-dcpa)2}(μ2-hmt)}·5H2O}n(2)(Hpa=苯氧乙酸,Hdcpa=2,4-二氯苯氧乙酸,hmt=六亚甲基四胺)。2个配合物均用元素分析、红外光谱、X射线单晶衍射及差热分析进行了表征。晶体结构分析表明,在配合物1中,4个苯氧乙酸根桥联2个Cu2+形成[Cu2(COO)4]双核结构,相邻的[Cu2(COO)4]双核单元由六亚甲基四胺桥联成一维的"zigzag"链;在配合物2中,6个2,4-二氯苯氧乙酸根和2个OH-桥联6个Zn2+形成六核{[Zn3(dcpa)4(μ3-OH)]2(μ2-dcpa)2}结构单元,然后相邻的六核单元由2个六亚甲基四胺桥联成一维双链结构。  相似文献   

11.
A series of new oxo-vanadium(IV) complexes, [VOCl0.69(OH)0.31 (2,2′-bipy)2]Cl·2H2O (1, 2,2′-bipy?=?2,2′-bipyridine) [(VO)2Cl4(4,4'-bipy)3 (H2O)2] (2, 4,4'-bipy?=?4,4'-bipyridine), [VO(ida)(H2O)]n (3, H2ida?=?iminodiacetic acid), and [(VO)2(oa)4]n·4n(H3O)·n(H2O) (4, H2oa?=?oxalic acid), have been synthesized and structurally characterized. 1 contains a [VOCl0.69(OH)0.31(2,2′-bipy)2]+ cation, Cl anion and two free H2O molecules. 2 exhibits a binuclear centrosymmetric moiety built up from two [VOCl2(4,4'-bipy)(H2O)] units and one bridging 4,4'-bipy ligand, which provides a rare example of a 4,4'-bipy molecule acting as monodentate ligand. 3 displays a neutral chain [VO(ida)(H2O)]n constructed by the linkages of [VO(H2O)]2+ units and ida2? bridging ligands, while 4 offers the only example of three kinds of oa2- ligands coexisting within the same anionic chain [(VO)2(oa)44-]n. Their spectroscopic properties were investigated, and the magnetic susceptibility of 4 shows antiferromagnetic behavior.  相似文献   

12.
Three 3-D coordination polymers, [Cu(cca)(4,4′-bipy)]n (1), [Co3(pda)3(1,10′-phen)2]n (2), and [Co(pda)(1,10′-phen)]n (3), have been synthesized from 4-carboxycinnamic acid (cca), 1,4′-phenylenediacrylic acid (pda), 4,4′-bipyridine (4,4′-bipy), 1,10′-phenanthroline (1,10′-phen), and Cu and Co salts under different conditions. The X-ray crystal structures of these three complexes are presented. Complex 1 exhibits a threefold 3-D α-Po interpenetration network. Complex 2 with a 3-D framework with six-connected single α-Po framework constructed from Co3 unit has been synthesized and characterized. Complex 3 shows a 3-D framework with bcu topology composed of 1-D rod-shaped secondary building units. Furthermore, the photocatalytic properties of 2 were studied. When excited by UV light, 2 exhibits photocatalytic activity, in 300?min, about 71% Rhodamine B decomposes.  相似文献   

13.
Assembly of 5-sulfosalicylic acid (H3L) and d10 transition metal ions (CdII, AgI) with the neutral N-donor ligands produces five new complexes: [Cd2(HL)2(4,4′-bipy)3]n·2nH2O (1), {[Cd2(μ2-HCO2)2(4,4′-bipy)2(H2O)4][Cd(HL)2(4,4′-bipy)(H2O)2]}n (2), {[Cd(4,4′-bipy)(H2O)4][HL]·H2O}n (3), [Cd(HL)(dpp)2(H2O)]n·4nH2O (4), {[Ag(4,4′-bipy)][Hhbs]}n (5) (4,4′-bipy=4,4′-bipyridine, dpp=1,3-di(pyridin-4-yl)propane, H2hbs=4-hydroxybenzenesulfonic acid, the decarboxylation product of H3L). Complex 1 adopts a 5-connected 3D bilayer topology. Complex 2 has the herring-bone and ladder chain, which are extended to a 3D network via hydrogen bonding. In 3–4 complexes, 3 is a 3D supermolecular structure formed by polymeric chains and 2D network of HL2−, while 4 gives the double-stranded chains. In 5, ladder arrays are stacked with the 2D networks of Hhbs anions in an –ABAB– sequence. Complexes 1–4 display green luminescences in solid state at room temperature, while emission spectra of 3 and 4 show obvious blue-shifts at low temperature.  相似文献   

14.
Abstract

Hydrothermal reaction of Zn(NO3)2 · 6?H2O with 2-carboxyethyl(phenyl)phosphinate (H2L) and 4,4'-bipyridine (4,4′-bipy) led to a novel zinc(II) carboxyphosphinate [ZnL(4,4′-bipy)0.5]n (1). The zinc ion is tetrahedrally coordinated by two phosphinate oxygen atoms, one carboxylate oxygen atom, and one nitrogen atom of 4,4′-bipy ligand. The L2- ligand and zinc ion can be seen as three- and four-connected nodes, respectively. Compound 1 shows a layered network with (3,4)-connected topology. It exhibits a broad blue fluorescent emission band at 459?nm, which can be attributed to 4,4′-bipy intraligand emission as well as to H2L emission. It is a diamagnetic system between 300?K and 11?K.  相似文献   

15.
Four new compounds, [Mn(HL)(phen)2(H2O)] (1), [Ni(HL)(phen)2(H2O)] (2), [Zn(HL)(4,4′-bipy)1.5(H2O)] n ?·?2nH2O (3) and [Zn2(HL)2(H2O)6] (4), have been synthesized from an asymmetric semi-rigid V-shaped multicarboxylate 4-(4-carboxy-phenoxy)-phthalic acid (H3L) with 1,10-phenanthroline (phen), or 4,4′-bipyridine (4,4′-bipy) as auxiliary ligands. Single-crystal X-ray diffraction analysis reveals that 1, 2 and 4 have 0-D structures with 3-D supramolecular frameworks formed by intermolecular hydrogen bonds. Compound 3 shows a 1-D infinite ribbon bridged by 4,4′-bipy, which further forms a 3-D supramolecular architecture by π–π stacking interactions and hydrogen bonds. Thermal stabilities of 14 and luminescence properties of 3 and 4 have also been investigated.  相似文献   

16.
Three new metal coordination polymers, [Mn(Hdpa)2(4,4′-bipy)2] n (1), [Mn(dpa)(1,10-phen)(H2O)] n (2), and [Mn(dpa)(2,2′-bipy)] n (3) (H2dpa = 2,4-biphenyl-dicarboxylic acid, 4,4′-bipy = 4,4′-bipyridine, 1,10-phen = 1,10-phenanthroline, and 2,2′-bipy = 2,2′-bipyridine), have been synthesized and characterized by elemental analysis, IR, and X-ray diffraction. Single-crystal X-ray analyses reveal that 2,4′-diphenic acid is a bridging ligand, exhibiting three coordination modes to link metal ions: μ 1-η 1: η 1/μ 0-η 0: η 0; μ 2-η 2: η 0/μ 1-η 1: η 0; and μ 2-η 1: η 1/μ 2-η 1: η 1. Intermolecular hydrogen bonds in 1 lead to a zigzag chain. In 2, the 2-D supramolecular arrays extended along b-axis through π–π interactions between 1,10-phen. The dinuclear paddle-wheel second building units (SBUs) constructed by four dpa2? ligands in 3 are linked by dpa2? into double-strand chains. The fluorescence of H2dpa and 13 are also determined.  相似文献   

17.
Three inorganic–organic hybrid materials based on Keggin-type polyoxometalates (POMs), [CuII2(phen)2(4,4′-bipy)(H4,4′-bipy)2(H2O)2][PMo12O40]2·2H2O (1), [CuII(phen)2(H4,4′bipy)][PW12O40]·H2O (2), and [CuII2(phen)2(4,4′-bipy)(BW12O40)(H2O)2](H24,4′-bipy)0.5·3H2O (3) (phen = 1,10-phenanthroline, 4,4′-bipy = 4,4′-bipyridine), were synthesized using different POMs in the hydrothermal conditions. Compounds 1–3 were characterized by single-crystal X-ray diffraction, IR spectra, elemental analyses, powder X-ray diffraction analyses, and thermogravimetric analyses. Compound 1 presents a two-dimensional (2-D) network containing the Keggin-type [PMo12O40]3? anion and dinuclear metal–organic units [CuII2(phen)2(4,4′-bipy)(H4,4′-bipy)2(H2O)2]3+. Compound 2 is a 2-D architecture constructed from a [PW12O40]3? and mononuclear metal–organic units [CuII(phen)2(H4,4′-bipy)]3+. In 3, the [BW12O40]5? anions link [CuII2(phen)2(4,4′-bipy)] units to form a one-dimensional (1-D) chain [CuII2(phen)2(4,4′-bipy)(BW12O40)(H2O)2]; the 1-D chain connects with protonated 4,4′-bipy ligands and lattice waters, yielding a 2-D layer. Fluorescence spectra, UV–vis spectra, and electrochemical properties of 1–3 have been investigated.  相似文献   

18.
将过渡金属配合物阳离子([M(DETA)2]n+(M=Cu2+,Ni2+,Co3+;DETA=Diethylenetriamine,二乙烯三胺)作为客体插入层状MnPS3层间得到了相应的3个夹层化合物。通过X-射线粉末衍射、元素分析和红外光谱对夹层化合物的结构进行了表征。结果表明,与主体MnPS3 0.65 nm的层间距相比较,夹层化合物(Mn0.88PS3[Cu(DETA)2]0.12)的层间距扩大了0.32 nm,由此推测客体[Cu(DETA)2]2+在层间以平面四方的配位形式存在,而另2个夹层化合物(Mn0.79PS3[Ni(DETA)2]0.21和Mn0.74PS3[Co(DETA)2]0.17)的层间距扩大了0.48 nm,说明客体[(M(DETA)2]n+,M=Co3+,Ni2+) 在主体层间以八面体配位形式存在。磁性测试结果表明过渡金属离子[(M(DETA)2]n+(M=Cu2+,Co3+)的插入能引起主体MnPS3的磁性在35~40 K发生由顺磁向亚铁磁性的转变并表现自发磁化,而客体[Ni(DETA)2]2+却使夹层化合物的反铁磁相互作用增强,抑制了自发磁化的发生。  相似文献   

19.
Five metal imidazole dicarboxylate-based compounds, {[Zn3(MIDC)2(4,4′-bipy)3](4,4′-bipy)·8H2O}n (1), {[Co3(MIDC)2(4,4′-bipy)3](4,4′-bipy)·6H2O}n (2), {[Co3(MIDC)2(py)2(H2O)2]}n (3), {[Mn6(MIDC)4(py)5(H2O)4]}n (4), and {[Mn3(MIDC)2(Phen)3(H2O)2]}n (5) (H3MIDC = 2-methyl-1H-imidazole-4,5-dicarboxylic acid; 4,4′-bipy = 4,4′-bipyridine; py = pyridine; Phen = 1,10-phenanthroline), have been synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. We control the coordination modes of H3MIDC via hydrazine and obtained a series of coordination compounds containing honeycomb-like [M3(MIDC)2]n layers. We also investigated the effects of different neutral terminal or bridging ligands on [M3(MIDC)2]n layers. Coplanar [M3(MIDC)2]n layers and 4,4-bipy were used to construct 3-D frameworks of 1 and 2. Puckered [M3(MIDC)2]n layers were found in 3–5; 4 is the first [M3(L)2]n layer structure with two crests and troughs during each period (L = imidazole-4,5-dicarboxylic acid or its analog). Compound 5 is the first puckered [M3(L)2]n layer structure decorated by chelating neutral ligands. Compound 1 exhibits weak blue photoluminescence in the solid state at room temperature. Variable-temperature magnetic susceptibility measurements of 2–5 indicate strong antiferromagnetic interactions.  相似文献   

20.
By hydrothermal reactions of a newly designed ligand, 2-(p-tert-butylphenyl)-1H-imidazole-4,5-dicarboxylic acid (H3BuPhIDC) with Cd(II) or Zn(II), three metal-organic frameworks, [Cd(μ3-HBuPhIDC)(H2O)]·2H2O (1), [Cd(μ3-HBuPhIDC)(4,4′-bipy)0.5] (4,4′-bipy = 4,4′-bipyridine) (2), and [Zn23-HBuPhIDC)2(CH3OH)2] (3), have been obtained and characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. In 1, small countless diamond grids form a mesh structure and then are bridged through μ3-HBuPhIDC2? linkers building a 3-D framework. Compared with 1, 4,4′-bipy participates in the construction of a 3-D structure of 2. Polymer 3 shows an interesting 3-D open architecture, which contains infinite 1-D octagonal channels built by left- and right-handed helical chains. Thermal and solid-state photoluminescence properties of the polymers have been investigated.  相似文献   

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