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1.
[Co2(TTBT)4(1,2-BDC)2] n ?·?4nH2O (1), [Pb2(TTBT)2(1,3-BDC)2] n ?·?nTTBT?·?2nH2O (2), [Fe(TTBT)(1,4-BDC)(H2O)] n (3), and [Zn(TTBT)(1,4-BDC)(H2O)] n (4) have been hydrothermally synthesized by self-assembly of TTBT (TTBT?=?10,11,12,13-tetrahydro-4,5,9,14-tetraaza-benzo[b]triphenylene), benzene-dicarboxylic acid ligands 1,2-H2BDC, 1,3-H2BDC or 1,4-H2BDC (1,2-H2BDC?=?1,2-benzenedicarboxylic acid, 1,3-H2BDC?=?1,3-benzenedicarboxylic acid, 1,4-H2BDC?=?1,4-benzenedicarboxylic acid), and various metal salts. Compound 1 has dinuclear cluster units, four dimeric Co2 units connected to form a 32-membered ring via weak offset π–π interactions, which are further stacked via strong π–π interactions to form a 3-D supramolecular framework. Complex 2 contains 2-D layers with rhombohedral grids, which are connected to a 3-D structure by π–π interactions. 3 and 4 feature 1-D infinite chains, which are further extended by strong π–π interactions and O–H···O hydrogen bonds resulting in 3-D supramolecular architectures. The photoluminescent properties of 2 and 4 have also been investigated.  相似文献   

2.
Reactions of fresh M(OH)2 (M = Zn2+, Cd2+) precipitate and (RS)-2-methylglutaric acid (H2MGL), 2,2′-bipyridine (bipy), or 1,10-phenanthroline (phen) in aqueous solution at 50°C afforded four new metal–organic complexes [Zn2(bipy)2(H2O)2(MGL)2] (1), [Zn2(phen)2(H2O)(MGL)2] (2), [Cd(bipy)(H2O)(MGL)] · 3H2O (3), and [Cd(phen)(H2O)(MGL)] · 2H2O (4), which were characterized by single crystal X-ray diffraction, IR spectra, TG/DTA analysis as well as fluorescence spectra. In 1, the [Zn(bipy)(H2O)]2+ moieties are linked by R- and S-2-methylglutarate anions to build up the centrosymmetric dinuclear [Zn2(bipy)2(H2O)2(MGL)2] molecules. In 2, the 1-D ribbon-like chains [Zn2(phen)2(H2O)(MGL)2] n can be visualized as from centrosymmetric dinuclear [Zn2(phen)2(H2O)2(MGL)2] units sharing common aqua ligands. Both 3 and 4 exhibit 1-D chains resulting from [Cd(bipy)(H2O)]2+ and [Cd(phen)(H2O)]2+, respectively, bridged alternately by R- and S-2-methylglutarate anions in bis-chelating fashion. The intermolecular and interchain π···π stacking interactions form supramolecular assemblies in 1 and 1-D chains in 24 into 2-D layers. The hydrogen bonded lattice H2O molecules are sandwiched between 2-D layers in 3 and 4. Fluorescence spectra of 14 exhibit LLCT π → π* transitions.  相似文献   

3.
Two complexes, [Cd(ip–OH)(H2biim)(H2O)][Cd(ip–OH)(H2biim)(H2O)3]·8(H2O) (1) and [Cd(Himdc)(H2biim)] n (2) (H2ip–OH?=?5-hydroxylisophthalic acid, H2biim?=?2,2’-biimidazolate, H3imdc?=?4,5-imidazoledicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. 1 is a 3-D supramolecular network constructed by 0-D and 1-D motifs through hydrogen bonds and π?π interactions. Complex 2 is a 1-D zigzag polymeric coordination chain and the chains are connected to form a 3-D supramolecular network by hydrogen bonds. The complexes were characterized by elemental and thermogravimetric analyses. Fluorescence was also investigated.  相似文献   

4.
Reactions of Zn(II) salts, 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (HIPT) and 2-mercaptobenzoic acid or 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H3PrIDC), result in two mixed-ligand coordination polymers (CPs), [Zn2(IPT)(DSDB)(OH)]n (H2DSDB = 2,2′-disulfanediyldibenzoic acid, 1) and [Zn2(IPT)(PrIDC)(H2O)]n (H3PrIDC = 2-propyl-1H-imidazole-4,5-dicarboxylic acid, 2). Compound 1 possesses a 2-D structure built by 1-D [Zn(IPT)]n chains and DSDB2? connectors, in which the DSDB2? is generated via in situ reaction from 2-mercaptobenzoic acid. It displays a new intricate 4-nodal {3·4·6·7·8·9}{3·6·7·8·9·10}{3·8·9}{4·6·8} topology. Compound 2 displays a 3-D framework with new 3-connected topology with Schläfli symbol of (4·8·10) (8·122), in which the 1-D Zn-carboxylate chains were bridged by 3-connected IPT? ligands. The thermal stabilities and luminescence properties of 1 and 2 have also been studied. The compounds exhibit intense solid-state fluorescent emissions at room temperature.  相似文献   

5.
A new ligand, N-P-acetamidobenzenesulfonyl-glycine acid (abbreviated as abglyH2), and three transition metal complexes [Mn(abglyH)2(bipy)(H2O)2] n (1), [Mn(abglyH)2(bipy)2(H2O)2] (2) and [Zn(abglyH)2(H2O)4] (3) (bipy=4,4′-bipyridine) have been synthesized under mild conditions and characterized by IR, elemental analysis and X-ray diffraction analysis. Compound 1 exhibits a 1-D linear chain, which is further connected to a 3-D supramolecular network through various kinds of hydrogen bonds and p–π stacking interactions. 2 and 3 are monomeric compounds, and 2 is assembled by intermolecular hydrogen bonds and CH ···?π?interactions into a 3-D supramolecular network, while 3 is extended into a 2-D supramolecular network through hydrogen bonds. Fluorescent analysis shows that 3 has an emissive maximum at 353 nm in the solid state at room temperature.  相似文献   

6.
Four cobalt(II) coordination polymers, [Co2(oba)2(1,2-bix)2]n (1), [Co(oba)(1,3-bix)]n (2), {[Co4(oba)4(1,4-bix)4]·6H2O}n (3), and {[Co6(oba)6(1,4-bix)6]·2H2oba·3DMF·11H2O}n (4), where H2oba?=?4,4′-oxybis(benzoic acid), DMF = N,N-Dimethyl formamide, and 1,n-bix?=?1,n-bis(imidazol-l-yl-methyl)benzene (n?=?2, 3, 4), have been synthesized. These compounds were structurally characterized by single-crystal X-ray crystallography, IR spectroscopy, and thermogravimetric analysis. Compound 1 exhibits a 2-D nano square grid (4,4) network, while 2 features a 2-D structure with two distinct left- and right-handed helical chains. Compound 3 possesses a doubly interpenetrated double-layered framework structure. The structure of 4 is comprised of 1-D chains of rings. The structural differences reveal that the flexible dicarboxylate and neutral bis(imidazole) are effective building blocks in constructing coordination polymers with diverse architectures.  相似文献   

7.
Three new complexes: [Cd(btaa)(bipy)(CH3COO) · H2O] n (1), [Ni(btaa)2(H2O)4 · 6H2O] n (2), and [Mn(btaa)2(H2O)2] n (3) (bipy = 2,2′-bipyridine, Hbtaa = 1H-benzotriazole-1-acetic acid) were prepared and characterized by IR, elemental analyses, thermogravimetric analyses, and single-crystal X-ray analyses. In 1, cadmium ions are linked by btaa ligands into 1-D linear chains; the chains are extended into layers through C–H ··· O hydrogen bonds and π–π stacking interactions. Complex 2 is a mononuclear structure, extended to a 3-D network through multiple intermolecular hydrogen bonds. In 3, manganese is bridged by carboxylate groups of btaa in the syn–skew bidentate mode in two directions to form a 2-D grid-like framework with a (4, 4) topology. The solid-state fluorescence spectrum of 1 shows that the excitation peak is at 355 nm while the maximum emission peak is at 424 nm.  相似文献   

8.
{[Cu2(btm)2(Hbtc)(H2btc)2(H2O)]·9.5H2O}n (1), [Cu(bte)(H2btc)2]n (2) {[Cu(btp)(H2btc)2]·0.25H2O}n (3) (btm?=?bis(1,2,4-triazol-1-yl)methane, bte?=?bis(1,2,4-triazol-1-yl)ethane, btp?=?bis(1,2,4-triazol-1-yl)propane, H3btc?=?benzene-1, 3, 5-tricarboxylic acid) have been synthesized and structurally characterized. 1 features a 1-D double chain, which is interconnected by classical hydrogen-bonding (O–H?O) and ππ interactions to lead to a 3-D supramolecular architecture. 2 and 3 are both 1-D single chains, which are interconnected by ππ interactions to 2-D layer architectures. Elemental analysis, XRD, IR, TG and EPR spectra have been carried out and discussed.  相似文献   

9.
A series of transition metal (Zn, Cu, Mn) complexes with chelidamic acid (2,6-dicarboxy-4-hydroxypyridine, H3CAM) and 4,4′-bipyridine (bipy), [Zn2(bipy)Cl2] n (1), {[Zn2(HCAM)(H2CAM)2]?·?(bipy)?·?3.5H2O} n (2), [Mn3(HCAM)3(H2O)7]?·?(bipy)?·?3H2O (3), [Mn2(HCAM)2(bipy)?·?(H2O)2]?·?4H2O (4), [Cu2(HCAM)2(bipy)?·?(H2O)2]?·?4H2O (5), and Cu2(HCAM)2(bipy)?·?(H2O)2 (6), have been synthesized by hydrothermal or solution methods and characterized by single-crystal X-ray diffraction. The structural analyses reveal that 1 exhibits a zigzag chain of Zn(II), Cl?, and 4,4′-bipyridine. In 2, a 1-D polymeric [Zn2(HCAM)(H2CAM)2] n chain and a discrete 4,4′-bipyridine assemble into a 2-D supramolecular network via H-bonds. Complex 3 consists of asymmetric units of Mn3(HCAM)3(H2O)7 that are linked by hydrogen bonds to form a 2-D H-bonded network. Complexes 46 are isomorphous and possess discrete structures. The photoluminescent properties of 16 at room temperature were studied.  相似文献   

10.
A series of Cu(II) carboxylate complexes (carboxylate?=?2-fluorobenzoic acid (2-HFBA) or 4-fluorobenzoic acid (4-HFBA)) containing either one chelating 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and thermal analyses. In [Cu(bipy)(H2O)(2-FBA)2] (1), [Cu(bipy)(H2O)(4-FBA)2] (3), and [Cu(phen)(H2O)(2-FBA)2] (4), Cu is five-coordinate in a square pyramidal geometry and four-coordinate in [Cu(phen)(2-FBA)2] (2). The four complexes are extended into 1-D chains through hydrogen-bonding and π?···?π interactions in 1 and 4, only hydrogen-bonding in 2, and π?···?π interactions in 3. These contacts lead to aggregation and supramolecular self-assembly.  相似文献   

11.
Two 1-D and 3-D Ag(I) complexes involving 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid (H3PIDC) have been characterized by infrared spectrum, elemental analysis, and single-crystal X-ray diffraction. [Ag2(HPIDC)]n (1), synthesized under hydrothermal conditions, gave a 3-D framework; [Ag2(HPIDC)(MBI)]n (2) (MBI?=?2-methyl-1H-benzo[d]imidazole), with MBI as the second ligand, gave a 1-D zigzag chain and further formed a 3-D supramolecular structure through π···π interactions. The most interesting structural features of these complexes are the presence of C–H···Ag hydrogen bonding interactions and Ag···C weak interactions between the Ag centers and H3PIDC. Luminescence indicates that 2 has significantly stronger fluorescent emissions than 1 in the solid state at room temperature.  相似文献   

12.
Three zinc compounds assembled from a bithiophene dicarboxylic acid (H2DMTDC) and different N-donor co-ligands, [Zn(DMTDC)(bpt)(H2O)]n (1), {[Zn(DMTDC)(5,5-dmbpy)]·0.5DMF·1.5H2O}n (2), and {[Zn(DMTDC)(1,3-bimb)]·2DMF·H2O}n (3) (H2DMTDC?=?3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, bpt?=?4-amino-3,5-bis(4-pyridyl)1,2,4-triazole, 5,5′-dmbpy?=?5,5′-dimethyl-2,2′-bipyridyl, 1,3-bimb?=?1,3-bis(imidazol-1ylmethyl)benzene), were solvothermally synthesized and characterized. Compounds 1 and 2 are 1-D linear and zigzag chains with different supramolecular structures. In 1, adjacent chains form zipper-like structures through N–H?N interactions. In 2, however, chains in adjacent layers are stacked in an unusual unparallel level through C–H?O interactions. Compound 3 features a highly corrugated 2-D (4,4) layer and the layers are penetrated by each other to give 3-D polycatenations. Right- and left-handed helical Zn-bimb chains are arranged alternately within and between the layers, leading to mesomeric property of the whole network. Thermal stability and the decomposed products of all compounds were investigated. Luminescent properties of the ligands and compounds in the solid state at room temperature have also been explored. Moreover, the luminescence intensities of the compounds in different solvents are largely dependent on the solvent.  相似文献   

13.
Two metal-organic coordination polymers, [Co(tda)(ip)(H2O)2] n (1) and [Mn(tda)(ip)(H2O)] n (2) [H2tda?=?thiophene-2,5-dicarboxylic acid, ip?=?1H-imidazo[4,5-f][1,10]-phenanthroline], have been synthesized and characterized by elemental analyses, IR, PXRD, and X-ray diffraction. Single-crystal X-ray analyses reveal that 2,5-tda is a bridging ligand, exhibiting two coordination modes to link metal ions: μ11?:?η011?:?η0 and μ21?:?η111?:?η0. Compound 1 demonstrates a 1-D structure in which Co2+ centers are connected via tda anions into 1-D chains; the chains are further connected via hydrogen-bonding and π?···?π interactions. Compound 2 displays a 2-D structure in which tda connects two Mn ions forming a dinuclear molecule. In 2 the 3-D supramolecular structure arrays through hydrogen-bonding and π?···?π interactions. In addition, photoluminescence for 1 and 2 is also investigated in the solid state at room temperature.  相似文献   

14.
Three new Cd(II) complexes incorporating both 2-(1H-imidazol-1-methyl)-1H-benzimidazole (imb) and 1,4-benzenedicarboxylate (bdic2?), [CdCl(bdic)1/2(imb)2]n (1), {[Cd(bdic)(imb)(H2O)]·DMF·2H2O}n (2), and [Cd(bdic)(imb)]·3H2O}n (3), have been prepared and structurally characterized by single crystal X-ray diffraction. Bdic2? anions connect the?Cd-imb-Cd-imb?chains leading to a 2-D structure of 1. Bdic2?(A) and bdic2?(B) anions link the binuclear [Cd2(imb)2(H2O)2] units forming a 2-D structure of 2. Complex 3 features a 2-D structure involving supramolecular “double-layer” motifs. IR spectra and thermogravimetric curves are consistent with the results of the X-ray crystal structure analysis; 13 exhibit good fluorescence in the solid state at room temperature.  相似文献   

15.
Three coordination polymers built from planar tetranuclear clusters and H3sip ligands, Pb2Cl(sip)(bipy) (1), Pb2Br(sip)(H2O) (2), and Ni4(sip)2(pyz)2(H2O)8(OH)2·2H2O (3) (H3sip?=?5-sulfoisophthalic acid, bipy?=?2,2′-bipyridine, and pyz?=?pyrazine), have been hydrothermally synthesized and characterized by IR, TGA, and single-crystal X-ray diffraction. Compound 1 features a 2-D layer-like structure containing tetranuclear square [Pb4(SO3)2] clusters. Complex 2 has a 3-D open framework architecture constructed from tetranuclear cluster [Pb4Br2(SO3)2] inorganic building blocks. The tetranuclear units, [Ni4(OH)2(COO)4], in 3 are interlinked through carboxylates and µ2-pyz ligands to generate a 2-D layer structure. The connecting modes between tetranuclear clusters and organic ligands in the three compounds are discussed in this article. In the solid state at room temperature, yellow photoluminescence in 1 and 2 are observed.  相似文献   

16.
This work presents an investigation on the positions of the substituent and N-donor auxiliary chelating ligand (bipy/phen) effect on engineering of crystalline architectures of four Pb(II) complexes with a pair of methyl-substituted 3-sulfobenzoic isomers: [Pb(4-msba)(phen)(H2O)] (1), [Pb(4-msba)(bipy)(H2O)]·H2O (2), [Pb(5-msba)(phen)2]·9H2O (3), and [Pb2(5-msba)2(bipy)2(H2O)2] (4) (4/5-msba?=?4/5-methyl-3-sulfobenzoate, phen?=?1,10-phenanthroline and bipy?=?2,2′-bipyridine). The lead(II) ions exhibit hemidirected geometry in 1–4. The positions of the methyl as well as the auxiliary chelating ligands influence coordination modes of the sulfonates and thus determine the architectures. As the position of methyl in aromatic ring changes from 4 to 5, the structures change from 2-D sheet-like compounds for 1 and 2 to 0-D dimeric species for 3 and 4. A water cluster (H2O)18 exists in 3, which further assembles into a water tape with a new pattern T4(3)4(3)10(3)A4. Complex 3 loses crystallinity rapidly in the open air and turns into [Pb(5-msba)(phen)2]·2H2O (3A). Thermal stabilities and solid state fluorescent properties of 1, 2, 3A, and 4 have been studied.  相似文献   

17.
{[Pb(tsgluo)]?·?H2O} n (1), [Pb2(tsgluo)2(phen)2] (2), and [Pb2(tsgluo)2(bipy)2] (3) (H2tsgluo?=?N-p-tolylsulfonyl-L-glutamate, phen?=?1,10-phenanthroline, bipy?=?2,2′-pyridine) have been synthesized in the absence or presence of phen or 2,2′-bipy and structurally characterized by elemental analysis, IR, and X-ray crystallography. Single-crystal X-ray analyses reveal that tsgluo exhibits two coordination modes to link lead ions. Complex 1 gives a 2-D layer structure while 2 and 3 exhibit monomolecular structures; 3 is further connected into a double-chain structure by hydrogen bonds. Phen and 2,2′-bipy are very important for the crystal structure. Fluorescence of the compounds is also discussed.  相似文献   

18.
Reaction of Ln(NO3)3?·?6H2O with H2napn (H2napn?=?N,N′-ethylenebis(2-hydroxy-1-naphthylideneiminato)) and KSCN produces seven new coordination polymers, [La(H2napn)(SCN)(C2H5OH)2(NO3)2] n (1), [La(H2napn)2(SCN)(NO3)2] n (2), and [Ln(H2napn)1.5(NO3)3] n [Ln?=?La(3), Sm(4), Eu(5), Dy(6), Er(7)]. Crystal structure analysis reveals that H2napn functions as a bridging ligand, forming a 1-D chain polymer (1) and 2-D open-frameworks (27) with lanthanides. Each metal center of 17 is nine-coordinate. Lanthanide contraction is observed in 37.  相似文献   

19.
Three coordination compounds, {[Co(btrp)2(H2O)2]?·?NO3?·?H2O} n (1), {[Co(btrp)2(H2O)2]?·?H2O?·?2H2btc} n (2), and {[Co(btrp)3]?·?2ClO4} n (3) (btrp?=?1,3-bis(1,2,4-triazol-1-yl)propane; H3btc?=?benzene-1,3,5-tricarboxylic acid), have been prepared via solvothermal method and characterized by single-crystal X-ray diffraction and elemental analyses. Compound 1 possesses a 1-D double-stranded chain composed of ribbons of 20-membered cycles. Binuclear water clusters link adjacent nitrate anions to form a 1-D supramolecular helix in the structure. Compound 2 has a 1-D double-stranded chain wherein free H2btc ligands constitute 1-D negative chains through classical hydrogen-bonding interactions (O–H?···?O). Compound 3 exhibits a triple-stranded 1-D chain. For 13, 3-D supramolecular structures are consolidated by interchain weak hydrogen-bonding interactions as well as electrostatic interactions.  相似文献   

20.
Six transition metal coordination compounds with H2mand and different N-donor ligands, [Co(Hmand)2(2,2′-bipy)]·H2O (1), [Ni(Hmand)2(2,2′-bipy)]·H2O (2), [Ni(Hmand)2(bpe)] (3), [Zn(Hmand)2(2,4′-bipy)(H2O)]·2H2O (4), [Zn(Hmand)(bpe)(H2O)]n[(ClO4)]n·nH2O (5), and [Zn(Hmand)(4,4′-bipy)(H2O)]n[(ClO4)]n (6), were synthesized under different conditions (H2mand = (S)-(+)-mandelic acid, bpe = 1,2-di(4-pyridyl)ethane, 4,4′-bipy = 4,4′-bipyridine, 2,4′-bipy = 2,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine). Their structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, infrared spectra, thermogravimetric analysis, powder X-ray diffraction, and circular dichroism. Compounds 1 and 2 are isostructural (0-D structures), which are extended to supramolecular 1-D chains by hydrogen bonding. Compound 3 exhibits 1-D straight chain structures, which are further linked via hydrogen bond interactions to generate a 3-D supramolecular architecture. Compound 4 displays a discrete molecular unit. Neighboring units are further linked by hydrogen bonds and ππ interactions to form a 3-D supramolecular architecture. Compound 5 displays a 2-D undulated network, further extended into a 3-D supramolecular architecture through hydrogen bond interactions. Compound 6 possesses a 2-D sheet structure. Auxiliary ligands and counteranions play an important role in the formation of final frameworks, and the hydrogen-bonding interactions and ππ stacking interactions contributed to the formation of the diverse supramolecular architectures. Compounds 1, 2, 4, 5, and 6 crystallize in chiral space groups, with the circular dichroism spectra exhibiting positive cotton effects. Furthermore, the luminescent properties of 46 have been examined in the solid state at room temperature, and the different crystal structures influence emission spectra significantly.  相似文献   

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