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1.
The use of succinamic acid (H2sucm) in CuII/N,N′,N″-donor [2,2′:6′,2″-terpyridine (terpy), 2,6-bis(3,5-dimethylpyrazol-1-yl)pyridine (dmbppy)] reaction mixtures yielded compounds [Cu(Hsucm)(terpy)]n(ClO4)n (1), [Cu(Hsucm)(terpy)(MeOH)](ClO4) (2), [Cu2(Hsucm)2(terpy)2](ClO4)2 (3), [Cu(ClO4)2(terpy)(MeOH)] (4), [Cu(Hsucm)(dmbppy)]n(NO3)n·3nH2O (5.3nH2O), and [CuCl2(dmbppy)]·H2O (6·H2O). The succinamate(−1) ligand exists in four different coordination modes in the structures of 13 and 5, i.e., the μ2OO′:κO″ in 1 and 5 which involves asymmetric chelating coordination of the carboxylato group and ligation of the amide O-atom leading to 1D coordination polymers, the μ22OO′ in 3 which involves asymmetric chelating and bridging coordination of the carboxylato group, and the asymmetric chelating mode in 2. The primary amide group, either coordinated in 1 and 5, or uncoordinated in 2 and 3, participate in hydrogen bonding interactions, leading to interesting crystal structures. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the Hsucm ligands. The thermal decomposition of complex 5·3nH2O was monitored by TG/DTG and DTA measurements.  相似文献   

2.
The reaction of 4,4′-bipyridine (bipy), AgNO3 and 4-sulfobenzoate (4-sb) led to an unprecedented complex, {[Ag2(4,4′-bipy)2(H2O)2]·(1,4-bds)·(2H2O)}n (1), in which benzene-1,4-disulfonate (1,4-bds) was synthesized in situ. This does not happen in the similar 1,2-bis(4-pyridyl)ethylene (bpe) system, where the complex {[Ag2(bpe)2(H2O)2]·(4-sb)·3H2O}n (2) is formed. The same in situ reaction occurred when triphenylphosphine (PPh3) was added into the bipy and silver reaction solution, resulting in the complex [Ag2(PPh3)4(1,4-bds)]. 2DMF (3). Complex 4, {[Ag2(Ph3P)2(4-sb)(H2O)]·(H2O)}n, was synthesized similar to the synthesis of complex 3, without the presence of 4,4′-bipyridine. Complexes 1-4 were characterized by single-crystal X-ray analyses, elemental analyses, IR spectra, TG analyses, fluorescence studies and electric conductivity. Complexes 1 and 2 are cation-anion species. Complexes 3 and 4 are silver triphenylphosphine complexes, where the phenyl embrace interactions play important roles. In 3, the six-fold phenyl embrace (6PEs) connect the molecules into a 1-d hybrid zig-zag infinite chain. Complex 4 is a one-dimensional branch-like polymer containing a 1-d necklace-like backbone made up of an [Ag2(4-sb)(H2O)] unit and PPh3 ‘‘leaves”. Two new coordination modes for the 1,4-bds ligands and one for the 4-sb ligand are observed. Complexes 1-3 are semi-conductors, while complex 4 is an insulator.  相似文献   

3.
Reactions of 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid (H3PyIDC) with a series of Ln(III) ions affords ten coordination polymers, namely, {[Ln(H2PyIDC)(HPyIDC)(H2O)2]·H2O}n [Ln=Nd (1), Sm (2), Eu (3) and Gd (4)], {[Ln(HPyIDC)(H2O)3]·(H2PyIDC)·H2O}n [Ln=Gd (5), Tb (6), Dy (7), Ho (8) and Er (9)], and {[Y2(HPyIDC)2(H2O)5]·(bpy)·(NO3)2·3H2O}n (10) (bpy=4,4′-bipyridine). They exhibit three types of networks: complexes 1-4 are isomorphous coordination networks containing neutral 2D metal-organic layers, while complexes 5-9 are isomorphous, which consist of cationic metal-organic layers and anionic organic layers, and complex 10 is a 2D network built up from 4-connected HPyIDC2− anion and 4-connected Y(III) ions. In addition, thermogravimetric analyses and solid-state luminescent properties of the selected complexes are investigated. They exhibit intense, characteristic emissions in the visible region at room temperature.  相似文献   

4.
The hydrothermal reactions of Cd, Zn, or Cu(II) acetate salts with H2PHDA and BPP flexible ligands afford three new coordination polymers, including [Cd(PHDA)(BPP)(H2O)]n(1), [Zn(PHDA)(BPP)]n(2), and [Cu2(PHDA)2(BPP)]n(3) (H2PHDA=1,2-phenylenediacetic acid, BPP=1,3-bis(4-pyridyl)propane). The single-crystal X-ray diffractions reveal that all three complexes feature various metal carboxylate subunits extended further by the BPP ligands to form a diverse range of structures, displaying a remarked structural sensitivity to metal(II) cation. Complex 1 containing PHDA-bridged binuclear cadmium generates 1D double-stranded chain, complex 2 results in 2D→2D interpenetrated (4,4) grids, and complex 3 displays a 3D self-penetrated framework with 48668 rob topology. In addition, fluorescent analyses show that both 1 and 2 exhibit intense blue-violet photoluminescence in the solid state.  相似文献   

5.
A series of new triorganotin(IV) pyridinedicarboxylates [(C2H5)3NH][(Me3Sn)3(2,6-pdc)2(H2O)2] (1), [(C2H5)3NH][(Ph3Sn)3(2,6-pdc)2(H2O)2] (2), [(C2H5)3NH]{[(PhCH2)3Sn]3(2,6-pdc)2(H2O)2} (3), [Me3Sn(3,5-pdc)]n (4), [Ph3Sn(3,5-pdc)]n (5), [(PhCH2)3Sn(3,5-pdc)]n (6), [(Me3Sn)2(2,5-pdc)]n (7), [(Ph3Sn)2(2,5-pdc)]n (8) and {[(PhCH2)3Sn]2(2,5-pdc)}n (9) were synthesized by the reaction of trimethyltin(IV), triphenyltin(IV) or tribenzyltin(IV) chloride with 2,6(3,5 or 2,5)-H2pdc (pdc = pyridinedicarboxylate) when triethylamine was added. Complexes 1-9 have been characterized by elemental, IR, 1H, 13C and 119Sn NMR analyses. Among them complexes 1, 5 and 7 have also been characterized by X-ray crystallographic diffraction analyses. Complex 1 has a trinuclear structure and forms a 2D supramolecular structure due to the coordinated water molecules via hydrogen bonds to the pendant O atoms of the carboxyl groups and the N atoms derived of the pyridine ring. Complex 5 forms a 1D polymeric chain by the intermolecular Sn?N (N atom derived of pyridine ring) interactions. Complex 7 has a network structure where 2,5-pyridinedicarboxylate acts as a tetradentate ligand coordinated to trimethyltin(IV) ions.  相似文献   

6.
Four new coordination polymers of cadmium(II) with hexamethylenetetramine (htm) have been synthesized and characterized by routine physicochemical techniques as well as by X-ray single crystal structure analysis. They are [CdBr(htm)(SCN)(H2O)2·CH3OH]n (1), [CdI(htm)(SCN)(H2O)2·0.5(CH3OH)]n (2), [Cd2(htm)3(SCN)4(H2O)]n·nH2O (3) and [Cd3Br6(htm)2(H2O)5·(htm)(H2O)6]n (4). Complexes 1, 2 and 3 exhibit 1D polymeric structure and complex 4 shows a 2D undulated layered arrangement, containing Cd6(htm)6 hexagonal units as building block, which extended to a 3D supramolecular architecture through hydrogen bonding. Thorough thermal investigation suggest that as far as the thermal stability of Cd(II)-htm bond is concerned it attains the maximum in complex 1 and minimum in complex 4. In case of complex 3 the thermal study inferred that CdS end product was obtained at ∼730 °C, whereas in case of other complexes the thermally stable end product remained unidentified. Solid state fluorescence study shows that all the complexes are luminescent at room temperature except complex 3.  相似文献   

7.
Reactions of copper(II) sources with 1,2-bis(4-pyridyl)ethane (bpe) yielded metal-organic networks with diverse topologies and dimensionalities. Compounds [Cu(bpe)2(dmf)2]n(ClO4)2n·2ndmf (1·2ndmf), [Cu(bpe)2(dmf)2]n(ClO4)2n·3.5ndmf (2·3.5ndmf), [Cu(bpe)2(NO3)2]n·2nH2O (4·2nH2O) and [Cu2(bpe)(O2CMe)4]n·0.7nH2O (5·0.7nH2O) have been isolated by altering the copper(II) source, the reaction solvent and the crystallization process. Compounds 1·2ndmf and 2·3.5ndmf consist of cationic [Cu(bpe)2(dmf)2]2+ repeating units assembled to 1D and 2D (4,4) networks, respectively, and represent supramolecular isomers due to the conformational isomerism of the bridging bpe molecules. Compound 4·2nH2O consists of neutral mononuclear [Cu(dpe)2(NO3)2] repeating units assembled to inclined interpenetrating (4,4) sheets describing an overall entanglement that is 3D in nature, and compound 5·0.7nH2O consists of neutral dinuclear repeating units assembled to cross-linked 1D chains.  相似文献   

8.
Four copper(I) cyanide coordination polymers containing 2-(n-pyridyl)benzimidazole ligands, namely [Cu2(CN)(2-PyBIm)]n (1), [Cu2(CN)2(3-PyHBIm)]n (2), {[Cu3(CN)3(4-PyHBIm)4] · 2H2O}n (3) and [Cu5(CN)3(4-PyBIm)2]n (4), have been synthesized and characterized by X-ray crystallography. Complex 1 is a one-dimension coordination polymer in which 2-(2-pyridyl)benzimidazole is deprotonated and adopts a bridging tridentate coordination mode. Complex 2 has ladder-like structure in which 2-(3-pyridyl)benzimidazole does not deprotonate and acts as a bidentate bridge. Complex 3 displays a saddle-shaped helical chain constructed through μ2-cyanide group and the outstretched neutral 2-(4-pyridyl)benzimidazole monodentate ligand. Complex 4 shows two-dimension layer polymeric structure in which deprotonated 2-(4-pyridyl)benzimidazole acts as a tridentate bridging ligand. The cyanide groups in four complexes all act as bidentate bridging ligands. These complexes are thermal stable and display luminescence in the solid states.  相似文献   

9.
Based on the versatile ligand 3,5-bis(4-pyridyl)-1H-1,2,4-triazole (Hbpt) derived from an in situ metal/ligand reaction, a series of coordination compounds CoCl4(H3bpt)(H2O) (1), Cu(H2bpt)2(SO4)2(H2O)6 (2), [Ag(bpt)]n (3), [Co(Hbpt)(pa)]n (4), [Co(Hbpt)(pda)]n (5) and [Cu(Hbpt)(pda)(H2O)]n (6) have been constructed (pa = phthalate, pda = 1,3-phenylenediacetate). The structures of these targeted complexes have been characterized by X-ray single-crystal diffraction techniques. Structural analysis reveals that Hbpt adopts versatile coordination modes to arrange the metal ions in 0-D point, simple (4,4) layers and dinuclear core chains in 13, which are further extended via the benzenedicarboxylate connectors to give rise to a variety of coordination networks such as (4,4), (412 · 63), (64 · 82) topologies in 46. The supramolecular organization through hydrogen bonds is analyzed for these complexes and thermal stability of these crystalline materials has been explored by TG-DTG.  相似文献   

10.
[Cp4Fe4(CO)4] (1) reacts with p-BrC6H4Li and MeOH in sequence to afford the functionalized cluster [Cp3Fe4(CO)4(C5H4-p-C6H4Br)] (2), while the reaction of 2 with n-BuLi and MeOH produces [Cp2Fe4(CO)4(C5H4Bu)(C5H4-p-C6H4Br)] (3). The double cluster [Cp3Fe4(CO)4(C5H4)]2(p-C6H4) (4) has been prepared by treatment of [Cp4Fe4(CO)4] with p-C6H4Li2 and MeOH in sequence. The electrochemistry of 2 and 4, as well as the crystal structure of 4 have been investigated.  相似文献   

11.
Here we report the synthesis and characterization by X-ray diffraction, FTIR, UV-Vis and EPR spectroscopies, and the magnetic measurements of two new compounds: [Mn(NCS)2(bpe)2(H2O)2] (1) and [Fe(NCS)2(bpe)2(H2O)2] (2) (bpe = 1,2-bis(4-pyridyl)ethylene). Single-crystal structure analyses reveals discrete octahedral metal units that are assembled into 2D sheets through O-Hw?N(bpe) and O-Hw?S(thiocyanate) hydrogen bonds. The intermetallic M?M distances are 6.90 and 6.87 Å for 1 and 2, respectively. Supramolecular architectures are obtained by connections through H-bonds. Slight interactions are observed for compound 2.  相似文献   

12.
Four coordination polymers, [Zn(pda)(bpy)(H2O)]n·nH2O (1), [Cd(pda)(prz)(H2O)]n (2), [Co3(μ3-OH)2(pda)2(pyz)]n·2nH2O (3) and [Pr2(pda)3(H2O)2]n (4) (H2pda=1,3-phenylendiacetic acid, bpy=4,4′-bipyridine, prz=piperazine and pyz=pyrazine) have been hydrothermally synthesized and characterized. Complex 1 is a 1D wheel-like chain structure, which is further extended into a 3D metal-organic supramolecular framework by H-bonds and π-π stacking interactions. Complex 2 is a 1D ladder-like chain structure, which is also further extended into a 3D metal-organic supramolecular framework by H-bonds. Complex 3 possess a 2D sheet structure with infrequent two pairs of double-helix chains. Complex 4 features a 3D structure. Both 1 and 2 display strong blue fluorescent emission at room temperature. Magnetic susceptibility measurements of complexes 3 and 4 exhibit antiferromagnetic interactions between the nearest metal ions, with C=9.99 and 3.43 cm3 mol−1 K, and θ=−23.9 and −46.3 K, respectively.  相似文献   

13.
Two polyoxometalate (POM) supramolecular assemblies based on W18 clusters and the rigid organic trans-1,2-di-(4-pyridyl)-ethylen (bpe) have been synthesized and fully characterized, namely (H2bpe)3.5H2[SbW18O60]·5H2O (1), and (H2bpe)5[Ni4(AsW9O34)2(H2O)2]·3H2O (2). Compounds 1-2 are formed from organic bpe cations and different polytungstate anions: pseudo-Dawson-type [SbW18O60]9− in 1 and sandwich-type [Ni4(H2O)2(AsW9O34)2]10− in 2. Both of compounds 1-2 crystallize in a low-symmetrical space group of P-1 and consist of a complicated supramolecular network based on non-covalent intermolecular weak interactions, including hydrogen bonding and π···π stacking. The multipoint hydrogen bonding interactions constitute the structural feature in two supramolecular frameworks. The UV-vis, fluorescence and electrochemistry properties are also studied.  相似文献   

14.
5-Ferrocenylpyrimidine (FcPM) reacts with dinuclear copper(II) carboxylates ([Cu2(RCOO)4]; R = C6H5, C5H11, CH3) to produce one-dimensional coordination polymers [Cu2(C6H5COO)4(FcPM)]n (1), [Cu2(C5H11COO)4(FcPM)]n · nCH3CN (2), and a discrete tetranuclear complex [Cu2(CH3COO)4(FcPM)2] (3). Compounds 1 and 2 show similar zigzag chain structures, comprising alternate linking of FcPM and dinuclear copper(II) units, whereas the structure of 3 corresponds to the local structural motifs of 1 and 2. Reaction of FcPM with zinc salts (ZnX2; X = NO3, SCN) affords zinc-centered ferrocenyl cluster complexes, [Zn(NO3)2(FcPM)3] (4) and [Zn(SCN)2(FcPM)2] · 0.5H2O (5), with varying M:L ratios. FcPM acts as a bidentate ligand in 1 and 2, and as a monodentate ligand in the others.  相似文献   

15.
Reactions of different metal salts with 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) gave rise to five new complexes, namely [Cu4(CN)4(3-abpt)2]n (1), [CuBr(3-abpt)]n (2), [CuI(3-abpt)]n (3), [Cu3I3(3-abpt)]n (4) and [Cu(3-abpt)(SO4)(H2O)]n (5). Compounds 1, 3, 4 and 5 are all 2D structures. Compound 1 is a double-layered polymer with an uncommon 3-nodal 3-connected (103)(102.4)4 network, 3 shows a 2D square layered structure, 4 is also a double-layered polymer with 2-nodal 4-connected (3.4.5.62.7)2(3.42.52.7) network and 5 is a 2D structure which is ultimately stacked with an ABAB repeat pattern. Compound 2 is a 1D coordination polymer which exhibits a ladder-like network. The photoluminescence of 1-2 has also been investigated. The long emission lifetimes of 1-2 could be assigned to metal-to-ligand charge transfer triple excited states [MLCT].  相似文献   

16.
Addition of tri(2-furyl)phosphine, PFu3, to [Os3(CO)10(μ-H)2] at room temperature gives [HOs3(CO)10(PFu3)(μ-H)] (1), while in refluxing toluene the same reactants afford [Os3(CO)93-PFu2(C4H2O)}(μ-H)] (2) resulting from orthometallatation of a furyl ring. Reaction of PFu3 with [Os3(CO)10−n(NCMe)n] (n = 0, 1, 2) affords the substituted clusters [Os3(CO)12−n(PFu3)n] (n = 1-3) (3-5), the phosphine ligands occupying equatorial position in all cases. Heating [Os3(CO)11(PFu3)] (3) in refluxing octane gives [Os3(CO)93-PFu)(μ32-C4H2O)] (6) which results from both carbon-hydrogen and carbon-phosphorus bond activation and contains both μ32-furyne and furylphosphinidene ligands. All new clusters have been characterized by spectroscopic methods together with single crystal X-ray diffraction for 2, 3 and 6.  相似文献   

17.
Four new polymers, namely [Ni(-tsgluO)(2,4′-bipy)2(H2O)2]n·5nH2O (1), [Co(-tsgluO)(2,4′-bipy)2(H2O)2]n·5nH2O (2), [Ni(-tsgluO)(4,4′-bipy)]n·0.5nH2O (3), and [Co(-tsgluO)(4,4′-bipy)]n·0.5nH2O (4), where tsgluO2−=(+)-N-p-tolylsulfonyl-l-glutamate dianion, 2,4′-bipy=2,4′-bipyridine, and 4,4′-bipy=4,4'-bipyridine, have been prepared and structurally characterized. Compounds 1 and 2 are isostructural and mononuclear, and crystallize in the acentric monoclinic space group Cc, forming 1D chain structures. Compound 3 is also mononuclear, but crystallizes in the chiral space group P21, forming a homochiral 2D architecture. In contrast to the other complexes, compound 4 crystallizes in the space group P−1 and is composed of binuclear [Co2O6N2]n4− units, which give rise to a 2D bilayer framework. Moreover, compounds 1, 2, and 4 self-assemble to form 3D supramolecular structures through π-π stacking and hydrogen-bonding interactions, while compound 3 is further hydrogen-bonded to form 3D frameworks. We have demonstrated the influence of the central metal and bipyridine ligands on the framework chirality of the coordination complexes.  相似文献   

18.
The systematic investigation of the parameter space of the CuCl2/H2mal/phen reaction system in MeOH resulted in the isolation of seven different complexes either as mixtures or in pure form, six of which have been structurally characterized. The molar ratios of the reactants and the crystallization methods have been systematically varied, leading to the isolation of compounds [Cu(H2O)(phen)(mal)] (1), [Cu(MeOH)(phen)(mal)] (2), [Cu2Li2Cl2(phen)2(mal)2(MeOH)4] (3), [Cu2(phen)4(mal)][CuCl(phen)(mal)](OH) (4), [CuCl(phen)2]Cl (5), and [CuCl(phen)(mal)][CuCl(phen)2][Cu(phen)2(Hmal)]Cl (6). The coordination versatility of the malonato ligand has been confirmed by the presence of three different coordination modes and its two deprotonation states in compounds 16. Solution studies on methanolic solutions of 24 and 6 by mass spectrometry revealed the absence of parent ion peak and the presence of fragment ions of low relative abundance not previously found in their crystal structure, thus indicating decomposition and rearrangement/reorganization of the complexes in solution and confirming the dynamic character of their solutions. Compounds 3 and 4 have been also studied in the solid state by EPR spectroscopy and magnetic measurements.  相似文献   

19.
Nano-structures of two new Pb(II) three-dimensional coordination polymers, [Pb2(4-pyc)2I2(H2O)]n (1), {4-Hpyc = 4-pyridinecarboxilic acid} and [Pb(3-pyc)I]n (2), {3-Hpyc = 3-pyridinecarboxilic acid} were synthesized by sonochemical method. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and are three-dimensional coordination polymers. The thermal stability of compounds 1 and 2 both their bulk and nano-size were studied by thermal gravimetric and differential thermal analyses and compared. PbO block-structures were obtained by calcination of the nano-structures of compounds 1 and 2 at 400 °C.  相似文献   

20.
Four new coordination polymers {[Ni(HL)(H2O)]·H2O}n (1), {[Co(HL)(H2O)]·H2O}n (2), {[Co(HL)]·4H2O}n (3) and {[Zn(HL)]·2H2O·0.5C2H5OH}n (4) [H3L = 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid] have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses. Complexes 1 and 2 display (3, 3)-connected 2D network with (4, 82) topology. While 3 and 4 exhibit a binodal (3, 6)-connected 2D network with a Schläfli symbol (43)2(46, 66, 83). The complexes 14 show remarkable thermal stability and 4 exhibits blue fluorescence with maximum emission at 413 nm upon excitation at 362 nm in the solid state at room temperature. In addition, the magnetic measurements of 3 indicate that there are antiferromagnetic interactions between the neighboring Co(II) centers.  相似文献   

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