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1.
The zinc(II) coordination polymers [Zn(Htatb)(2,2′‐bipy) · (NMP) · H2O] ( 1 ) and [Zn3(tatb)2(2,2′‐bipy)3 · H2O] ( 2 ) (H3tatb = 4,4′,4′′‐s‐triazine‐2,4,6‐triyl‐tribenzoic acid; 2,2′‐bipy = 2,2′‐bipyridyl, NMP = N‐methyl‐2‐pyrrolidon), were synthesized hydrothermally, and characterized by infrared spectroscopy (IR), powder X‐ray diffraction (PXRD), and single‐crystal X‐ray diffraction. Both compounds 1 and 2 possess expectant low dimensional coordination structures, which further connected into interesting 3D networks by hydrogen bond and strong π–π interactions. Moreover, the thermal stabilities and fluorescent properties of 1 and 2 were investigated.  相似文献   

2.
The 2D CuII metal‐organic framework [Cu2(bptc)(H2O)4]n · 4nH2O ( 1 ) (H4bptc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid) was hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction and magnetic measurements. In the structure, bptc4– serves as a twisted Π‐shaped organic building block to connect paddlewheel [Cu2(COO)4] dinuclear units and mononuclear units through 2‐/2′‐carboxylate and 4‐/4′‐carboxylate, respectively. According to the magnetic analysis using a dimer‐plus‐monomer model, strong antiferromagnetic coupling is operative within the dinuclear unit (J = –311 cm–1 based on H = –J S 1 S 2), and the compound behaves like a mononuclear molecule at low temperature.  相似文献   

3.
Two new coordination polymers, {[Cd2(btc)(2,2′‐bpy)2] · H2O}n ( 1 ) and [Zn2(btc)(2,2′‐bpy)(H2O)]n ( 2 ) (H4btc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine), were synthesized hydrothermally under similar conditions and characterized by elemental analysis, IR spectra, TGA, and single‐crystal X‐ray diffraction analysis. In complexes 1 and 2 , the (btc)4– ligand acts as connectors to link metal ions to give a 2D bilayer network of 1 and a 3D metal‐organic framework of 2 , respectively. The differences in the structures are induced by diverging coordination modes of the (btc)4– ligand, which can be attributed to the difference metal ions in sizes. The results indicate that metal ions have significant effects on the formation and structures of the final complexes. Additionally, the fluorescent properties of the two complexes were also studied in the solid state at room temperature.  相似文献   

4.
Four new transitional metal supramolecular architectures, [Zn(cca)(2,2′‐bpy)]n · n(2,2′‐bpy) ( 1 ), [Cu(cca)(2,2′‐bpy)]n ( 2 ), [Zn(bpdc)(2,2′‐bpy)(H2O)]n · 0.5nDMF · 1.5nH2O ( 3 ), and [Co(bpdc)(2,2′‐bpy)(H2O)]n · nH2O ( 4 ) (H2cca = p‐carboxycinnamic acid; H2bpdc = 4,4′‐biphenyldicarboxylic acid; 2,2′‐bpy = 2,2′‐bipyridine) were synthesized by hydrothermal reactions and characterized by single crystal X‐ray diffraction, elemental analyses, and IR spectroscopy. Although the metal ions in these four compounds are bridged by linear dicarboxylic acid into 1D infinite chains, there are different π–π stacking interactions between the chains, which results in the formation of different 3D supramolecular networks. Compound 1 is of a 3D open‐framework with free 2,2′‐bpy molecules in the channels, whereas compound 2 is of a complicated 3D supramolecular network. Compounds 3 and 4 are isostructural. Both compounds have open‐frameworks.  相似文献   

5.
Four new lanthanide complexes [Ln(4‐EBA)3(5,5′‐DM‐2,2′‐bipy)]2·2C2H5OH (Ln = Ho ( 1 ), Tb ( 2 ), Er ( 3 )); [Ln(4‐EBA)3(4‐EBAH)(5,5′‐DM‐2,2′‐bipy)]2 (Ln = Eu( 4 ); 4‐EBA =4‐ethylbenzoate; 5,5′‐DM‐2,2′‐bipy =5,5′‐dimethy‐2,2′‐bipyridine; 4‐EBAH = 4‐ethylbenzoic acid) have been synthesized and characterized by elemental analysis and IR spectra. The single crystal results reveal that complexes 1 – 3 are isostructural. It is worth noting that the mole ratios of the carboxylate ligands and neutral ligands is 4:1 in complex 4 , which is different from the former and has been rarely reported. Nevertheless, all complexes are connected to form 1D chain by π ···π wake staking interactions. Additionally, the complexes 2 (Tb(III)) and 4 (Eu(III)) exhibit characteristic luminescent properties, indicating that ligands can be used as sensitizing chromophore in these systems. The thermal decomposition mechanism of the complexes has been investigated by TG/DSC–FTIR technology. Stacked plots of the FTIR spectra of the evolved gases show complexes broken down into H2O, CO2, and other gaseous molecules as well as the gaseous organic fragments. The studies on bacteriostatic activities of complexes show that four complexes have good bacteriostatic activities against Candida albicans but no bacteriostatic activity on Escherichia coli , and Staphylococcus aureus . Additionally, the complexes 1 to 3 have better bacteriostatic activities on Candida albicans than complex 4 .  相似文献   

6.
Slow diffusion reaction of 2,2′‐dithiodibenzoic acid (dtdb) with CuCl2 in the presence of N‐donor ligands results in the formation of different coordination polymers where both S–S and C–S scission and oxidation of S is observed. X‐ray diffraction analysis of [Cu(tdb)(phen)(H2O)]2 · 2H2O.2DMF] ( 1 ), [Cu(tdb)(py)2(H2O)]2 ( 3 ), and [Cu(tdb)(bipy)(H2O)]2 · 0.5H2O ( 4 ) (tdb = thiodibenzoic acid, phen = phenanthroline, py = pyridine, bipy = 2,2′‐bipyridine) show that the metal ions are coordinated to the carboxylate oxygen atoms of the in situ generated tdb ligand in a monodenate fashion. In [Cu(phen)(SO4)2(H2O)2]n ( 2 ) and [Cu(bipy)(SO4)2(H2O)2]n ( 5 ), the sulfur is oxidized to sulfate ions prior to coordination with the metal. Complex 1 has a dimeric structure with π–π interactions between the phen ligands, whereas 3 and 4 form 1D polymeric chains.  相似文献   

7.
Three cobalt(II) coordination polymers, [Co2(tatb)2(2,2′‐bipy)2 (H2O)2 · DMA · 2H2O] ( 1 ), [Co2(tatb)2(1,10‐phen)2(H2O)2 · 2H2O] ( 2 ) and [Co(tatb)(1,3‐dpp) · H2O] ( 3 ) (H3tatb = 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid; 2,2′‐bipy = 2,2′‐bipyridyl; 1,10‐phen = 1,10‐phenanthroline; 1,3‐dpp = 1,3‐bis(pyridin‐4‐yl)propane), were synthesized solvothermally and characterized by single‐crystal and powder X‐ray diffraction (PXRD), as well as IR spectroscopy. Complexes 1 and 2 exhibit 1D double‐chain structures, which further connect into interesting 3D networks by hydrogen bond and strong π–π interactions. Complex 3 possesses 2D 44‐sql topology, which is packed parallel in an AA fashion. Moreover, thermal stability properties and photoluminescence properties of 1 , 2 and 3 were also investigated.  相似文献   

8.
Three novel lanthanide complexes [Er (3,4‐DMBA)3(5,5′‐DM‐2,2′‐bipy)(H2O)] ( 1 ); [Tb2 (3,4‐DMBA)6(5,5′‐DM‐2,2′‐bipy)2(H2O)] ( 2 ); [Eu (3,4‐DMBA)3(3,4‐DMHBA)(5,5′‐DM‐2,2′‐bipy)]2 ( 3 ) (3,4‐DMHBA = 3,4‐dimethylbenzoic acid, 5,5′‐DM‐2,2′‐bipy =5,5′‐dimethyl‐2,2′‐bipyridine) were successfully synthesized via conventional solution method at room temperature and structurally characterized by single crystal diffraction. The structures of the complexes 1 – 3 were confirmed on the basis of elemental analysis, coordination titration analysis, IR and XRD. The molecular structures of complexes 2 and 3 are very particular: complex 2 has two same central metal ions but each metal ion has different coordination environment; in structure of the complex 3 , there are eight carboxylic acid ligands coordinated to the central metal ions, which have rarely been reported previously. The thermal decomposition mechanism of complexes 1 – 3 were investigated by the technology of simultaneous TG/DSC‐FTIR. The heat capacities of the complexes were recorded by means of DSC over the range of from 253.15 K to 345.15 K. The thermodynamic parameters, the smoothed values of heat capacities, enthalpy (HT‐H298.15K) and entropy (ST‐S298.15K) were also calculated. The bacteriostatic activities of the complexes were evaluated against Staphylococcus aureus, Escherichia coli and Candida albicans. What's more, the luminescence properties of complexes 2 and 3 were discussed, and their fluorescence lifetimes as well as the quantum yield of the Eu (III) were measured. To elucidate the energy transfer process of complexes 2 and 3, the energy levels of the relevant electronic states have been estimated.  相似文献   

9.
Two coordination polymers, {[Zn2(L)(bpy)] · 2H2O}n ( 1 ) and [Zn2(L)(bpe)]n ( 2 ) [H4L = terphenyl‐2,2′,4,4′‐tetracarboxylic acid, bpy = 4,4′‐bipyridine, and bpe = 1,2‐bis(4‐pyridyl)ethane], were hydrothermally synthesized under similar conditions and characterized by elemental analysis, IR spectroscopy, TGA, and single‐crystal X‐ray diffraction analysis. Compound 1 has a 3D framework containing Zn–O–C–O–Zn 1D chains. Compound 2 exhibits a 3D framework, which features tubular channels. The channels are occupied by bpe molecules. The differences in the structures demonstrate that the auxiliary dipyridyl‐containing ligand has a significant effect on the construction of the final framework. Additionally, the fluorescent properties of the two compounds were also studied in the solid state at room temperature.  相似文献   

10.
Five new coordination polymers, namely, [Ni2(L)2(4, 4′‐bipy)3)] · H2O]n ( 1 ), [Ni2(L)2(O) (bpp)2]n ( 2 ), [Zn(L)(bib)0.5]n ( 3 ), [Zn(L)(PyBIm)]n ( 4 ), and [Zn3(L)2(OH)(im)]n ( 5 ) [H2L = benzophenone‐2, 4′‐dicarboxylic acid, 4, 4′‐bipy = 4, 4′‐bipyridine, bpp = 1, 3‐bis(4‐pyridyl)propane, PyBIm = 2‐(4‐pyridyl)benzimidazole, and im = imidazole] were synthesized under hydrothermal conditions. Structure determination revealed that compound 1 is a 3D network and exhibits a 4‐connected metal‐organic framework with (42.63.8) topology, whereas compounds 2 , 3 , 4 , and 5 are two‐dimensional layer structures. In compounds 2 – 4 , dinuclear metal clusters are formed through carboxylic groups. In compound 5 , trinuclear metal clusters are formed through μ3‐OH and carboxylic groups. The carboxylic groups exhibit three coordination modes in compounds 1 – 5 : monodentately, bidentate‐chelating, and bis‐monodentately. Furthermore, the luminescent properties for compounds 3 , 4 , and 5 were investigated.  相似文献   

11.
RuII compounds have been universally investigated due to their unique physical and chemical properties. In this paper, a new RuII compound based on 2,2′‐bipy and Hpmtz [2,2′‐bipy = 2,2′‐bipyridine, Hpmtz = 5‐(2‐pyrimidyl)‐1H‐tetrazole], namely [Ru(2,2′‐bipy)2(pmtz)][PF6] · 0.5H2O was prepared and characterized by elemental analysis, IR and single‐crystal X‐ray diffraction. [Ru(2,2′‐bipy)2(pmtz)][PF6] · 0.5H2O shows a mononuclear structure and forms a three‐dimensional network by non‐classic hydrogen bonds. The ability of generation of ROS (reactive oxygen species) makes it has a low phototoxicity IC50 (half‐maximal inhibitory concentration) after Xenon lamp irradiation on Hela cells in vitro. The results demonstrate that [Ru(2,2′‐bipy)2(pmtz)][PF6] · 0.5H2O with high light toxicity and low dark toxicity may be a potential candidate for photodynamic therapy.  相似文献   

12.
Abstract. Two metal‐organic coordination polymers [Co(bmb)(btc)0.5]n( 1 ) and {[Zn(bmb)0.5(btc)0.5(H2O)] · 0.5bmb · H2O}n ( 2 ) [H4btc = benzene‐1, 2, 4, 5‐tetracarboxylic acid, bmb = 1, 4‐bis(2‐methylbenzimidazol‐1‐ylmethyl) benzene] were prepared under hydrothermal conditions. Single‐crystal X‐ray diffraction indicates that both complexes have a 2D framework structure with (4 · 62) (42 · 62 · 82) topology. Interestingly, the hydrogen bonds in 2 form a fascinating meso‐helix. The catalytic activity of 1 for oxidative coupling of 2, 6‐dimethylphenol (DMP) and the photoluminescence properties of 2 were investigated. Furthermore, the complexes were investigated by IR spectroscopy and thermogravimetric analysis.  相似文献   

13.
To investigate the influence of the non‐covalent interactions, such as hydrogen‐bonding, π–π packing and d10–d10 interactions in the supramolecular motifs, three cyanido‐bridged heterobimetallic discrete complexes {Mn(bipy)2(H2O)[Ag(CN)2]}[Ag(CN)2] ( 1 ), {Mn(phen)2(H2O)[Au(CN)2]}2[Au(CN)2]2 · 4H2O ( 2 ), and {Cd(bipy)2(H2O)[Au(CN)2]}[Au(CN)2] ( 3 ) (bipy = 2,2′‐bipyridine, and phen = 1,10‐phenanthroline), which are based on dicyanidometallate(I) groups with 1:2 stoichiometry of metal ions and 2,2′‐bipyridyl‐like co‐ligands were synthesized and structurally characterized. In compound 1 , hydrogen bonding and π–π interactions governed the supramolecular contacts. In compound 2 , the incorporation of aurophilic, hydrogen bonding and π–π interactions result in a 3D supramolecular network. In compound 3 , hydrogen bonding and π–π stacking interactions result in a 2D supramolecular layer. In the three complexes, hydrogen‐bonding, π–π packing and/or d10–d10 interactions can play important roles in increasing the dimensionality of supramolecular assemblies.  相似文献   

14.
Four metal‐organic frameworks (MOFs), {[Mn3.5L(OH)(HCOO)4(DMF)] · H2O} ( 1 ), {[In2.5L2O(OH)1.5(H2O)2] · DMF · CH3CN · 2H2O} ( 2 ), {[Pb4L3O(DMA)] · CH3CN} ( 3 ), and {[LaL(NO3)(DMF)2] · 2H2O} ( 4 ) were synthesized by utilizing the ligand 2,2′,6,6′‐tetramethoxy‐4,4′‐biphenyldicarboxylic acid (H2L) via solvothermal methods. All MOFs were characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction, thermogravimetric analysis, and infrared spectroscopy. In 1 , the Mn2+ ions are interconnected by formic groups in situ produced via DMF decomposition to form a rare 2D macrocyclic plane, which is further linked by L2– to construct the final 3D network. In 2 , 1D zip‐like infinite chain is formed and then interconnected to build the 3D framework. In 3 , a [Pb64‐O)2(O2C)10(DMA)2] cluster with a centrosymmetric [Pb64‐O)2]8+ octahedral core is formed in the 3D structure. In 4 , the La3+ ions are connected with each other through carboxylate groups of L2– to generate 1D zigzag chain, which is further linked by L2– to construct a 3D network with sra topology. Solid photoluminescence properties of 3 and 4 were also investigated.  相似文献   

15.
通过水热合成技术,一个新颖的基于Zn配合物修饰的Keggin型钴钨酸的有机-无机杂化化合物:[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O已经被合成,化合物通过红外光谱、热重分析和单晶X-射线衍射进行了表征。单晶X-射线衍射的结果显示标题化合物是由一个单支撑的{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2}6-多阴离子,三个[Zn(2,2’-bipy)3]2+阳离子和一个水分子构成。有趣的是[Zn(1)(2,2’-bipy)3]2+阳离子通过氢键连接在一起形成螺旋链。另外标题化合物在空气中是稳定的,并且在室温下显示了强的荧光。  相似文献   

16.
Chiral coordination polymers have attracted intense interest mainly due to their potential applications. Hence, two new chiral copper(II) coordination polymers {[Cu(tsgluO)(H2O)]2·3H2O}n ( 1 ) and [Cu(tsgluO)(2,2′‐bipy)]n ( 2 ) (H2tsglu?(+)‐N‐tosyl‐l‐glutamic acid; 2,2′‐bipy?2,2′‐bipyridine) were synthesized in the absence or presence of 2,2′‐bipy ligand and structurally characterized. A single crystal X‐ray diffraction study revealed that compound 1 consists of a paddle‐wheel dicopper(II) core, which links other equivalents via four tsgluO2? ligands to form a 1D double chain. Such a chain is further interconnected through weak π‐π stacking and hydrogen bonding interactions to form a 3D H‐bonded supramolecular structure with 1D channels hosting lattice water molecules. Whereas, compound 2 , containing the coordinating 2,2′‐bipy, gives rise to a ladder‐like 1D double chain. Antiferromagnetic interactions were observed in 1 and 2 .  相似文献   

17.
The hydrothermal reaction of Cd(NO3) · 4H2O with 4,4′‐bipyridine (bipy) and 3‐carboxyphenoxyacetatic acid (3‐H2CPOA) afforded a 3D metal‐organic framework (MOF) [Cd(3‐CPOA)(bipy)]n · 3.5nH2O, which was characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, and X‐ray diffraction. The single‐crystal structural analysis revealed that it has a Cds‐type topological network with 1D channels that contain encapsulated water molecular tapes.  相似文献   

18.
Three novel zinc complexes [Zn(dbsf)(H2O)2] ( 1 ), [Zn(dbsf)(2,2′‐bpy)(H2O)]·(i‐C3H7OH) ( 2 ) and [Zn(dbsf)(DMF)] ( 3 ) (H2dbsf = 4,4′‐dicarboxybiphenyl sulfone, 2,2′‐bpy = 2,2′‐bipyridine, i‐C3H7OH = iso‐propanol, DMF = N,N‐dimethylformamide) were first obtained and characterized by single crystal X‐ray crystallography. Although the results show that all the complexes 1–3 have one‐dimensional chains formed via coordination bonds, unique three‐dimensional supramolecular structures are formed due to different coordination modes and configuration of the dbsf2? ligand, hydrogen bonds and π–π interactions. Iso‐propanol molecules are in open channels of 2 while larger empty channels are formed in 3 . As compared with emission band of the free H2dbsf ligand, emission peaks of the complexes 1–3 are red‐shifted, and they show blue emission, which originates from enlarging conjugation upon coordination. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

19.
Two cobalt(II) coordination polymers, {[Co(μ‐4,4′‐bipy)(4,4′‐bipy)2(H2O)2]·(OH)3·(Me4N)·4,4′‐bipy·4H2O}n ( 1 ) and {[Co(μ‐4,4′‐bipy)(H2O)4]·suc·4H2O}n ( 2 ) (4,4′‐bipy = 4,4′‐bipyridine, suc = succinate dianions), were hydrothermally synthesized and structurally characterized by X‐ray diffraction analysis, UV‐Vis‐NIR, and ICP. The main structure feature common to the both polymers is presence of the infinite linear chains, [Co(μ‐4,4′‐bipy)(4,4′‐bipy)2(H2O)2]n ( 1 ) and [Co(μ‐4,4′‐bipy)(H2O)4]n ( 2 ), respectively. In 1 , the chains are further linked by the hydrogen‐bond and π‐π stacking interaction, producing extended layer structure. The 4,4′‐bipy molecules in 1 play three different roles. In 2 , the chains are linked into three‐dimensional network structure via complicated hydrogen bonding system. The variable temperature (2.0~300 K) magnetic susceptibility of 1 indicates a tendency of spin‐transition in the temperature range of 110 K to 22 K, which attributes to the transition of high‐spin to low‐spin from Co2+(d7) ion. Also, the result of surface photovoltage spectroscopy (SPS) reveals that the polymer 1 has significant photoelectric conversion property in the region of 300‐800 nm.  相似文献   

20.
Three inorganic‐organic hybrid frameworks [Mn(HIMDC)(4,4′‐bipyo)0.5(H2O)]n (1) , [Cd(H2IMDC)2(2,2′‐bipyo)] (2) and [Ca(HIMDC)(H2O)2·H2O]n (3) (H3IMDC = 4,5‐imidazoledicarboxylate; 4,4′‐bipyo = 4,4′‐bipyridine‐N,N′‐dioxide; 2,2′‐bipyo= 2,2′‐bipyridine‐N,N′‐dioxide) have been hydrothermally synthesized and characterized by the elemental analyses, IR spectra, TG analysis and the single crystal diffraction. Both compounds 1 and 3 exhibit 2D layers while 2 is a monomer. It is noteworthy that compound 2 exhibits strong fluorescent emission in the solid state at room temperature.  相似文献   

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