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1.
New conjugated oligomers, oligo(9,9‐didodecylfluorene‐bis‐sulphurdiimide), consisting of 9,9‐didodecylfluorene separated by ? N?S?N? moieties, are reported. These oligomers are stable purple solids under ambient conditions with absorption covering a broad spectral window in the UV‐vis range and a main broad peak centered at 555 nm with onset extending to 700 nm. These oligomers show an obviously longer conjugation length than its dimeric analogue, bis‐9,9‐didodecyl‐fluorene‐2‐sulfurdiimide that shows a band‐edge absorption centered at 484 nm with onset at 590 nm. The dimer and oligomers are soluble in a variety of organic solvents. Moreover, we found that the oligomer with an average repeating‐unit number of six could significantly quench the photoluminescence (PL) of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenylene vinylene] (MEH‐PPV) or poly(3‐hexylthiophene) (P3HT) in the solid state. More importantly, the composites of this oligomer with P3HT showed a nearly 10‐fold enhancement of the photocurrent, compared with that of P3HT itself. In addition, the PL of this oligomer could be quenched by the presence of phenyl‐C61‐butyric acid methyl ester (PCBM) in toluene. These results suggest the presence of photoinduced charge transfer in composites of these oligomers blended with an electronic partner that either donates or accepts electrons. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

2.
A series of novel toroidal cyclo‐2,9‐tris‐1,10‐phenanthroline macrocycles with an unusual hexaaza cavity are reported. Nickel‐mediated Yamamoto aryl–aryl coupling was found to be a versatile tool for the cyclotrimerization of functionalized 1,10‐phenathroline precursors. Due to the now improved processability, both liquid‐crystalline behavior in the bulk phase and two‐dimensional self‐assembly at the molecular level could be studied, for the first time, for a torand system. The macrocycles exhibited a strong affinity for the complexation of different metal cations, as evidenced by MALDI‐TOF analysis and spectroscopic methods. Experimental results were correlated to an extensive computational study of the cyclo‐2,9‐tris‐1,10‐phenanthroline cavity and its binding mode for metal cations. Due to the combination of several interesting features, toroidal macrocycles may find future applications in the field of ion and charge transport through molecular channels, as well as for chemical sensing and molecular writing in surface‐confined monolayers under STM conditions.  相似文献   

3.
A series of novel dysprosium coordination polymers were synthesized using new high‐Tg carboxyl‐containing polyaryletherketones (PEKs) as macromolecular ligands and a small molecule, 1,10‐phenanthroline, as co‐ligand. The FTIR, WAXD, and UV–Vis results indicated that the dysprosium ions were coordinated simultaneously with carboxyl group of PEKs and 1,10‐phenanthroline, and homogeneously distributed along the polymer backbone. These obtained dysprosium coordination polymers showed excellent film‐formation properties. Moreover, all the dysprosium coordination polymers could exhibit the intense characteristic emission of dysprosium ions under UV excitation. Meanwhile, the emission intensity increased with increasing dysprosium ion content, and no obvious fluorescence quenching happened at the Dy3+ ion content up to 10.71 wt%, which was attributed to the very rigid structure of PEK and synergistic coordination effect of PEK and 1,10‐phenanthroline. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

4.
Two one‐dimensional (1D) coordination polymers (CPs), namely catena‐poly[[[aqua(2,2′‐bipyridine‐κ2N,N′)(nitrato‐κO)copper(II)]‐μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ2N:N′] nitrate], {[Cu(NO3)(C10H8N2)(C13H14N2)(H2O)]·NO3}n ( 1 ), and catena‐poly[[[aqua(nitrato‐κO)(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ2N:N′] nitrate], {[Cu(NO3)(C12H8N2)(C13H14N2)(H2O)]·NO3}n ( 2 ), have been synthesized using [Cu(NO3)(NN)(H2O)2]NO3, where NN = 2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen), as a linker in a 1:1 molar ratio. The CPs were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray structure determination. The 1,3‐bis(pyridin‐4‐yl)propane (dpp) ligand acts as a bridging ligand, leading to the formation of a 1D polymer. The octahedral coordination sphere around copper consists of two N atoms from bpy for 1 or phen for 2 , two N atoms from dpp, one O atom from water and one O atom from a coordinated nitrate anion. Each structure contains two crystallographically independent chains in the asymmetric unit and the chains are linked via hydrogen bonds into a three‐dimensional network.  相似文献   

5.
Two zinc(II) and nickel(II) based coordination polymers, {[Zn(bibp)(MoO4)](H2O)2}n ( 1 ) [bibp = 4,4′‐bis(imidazol‐1‐yl)‐biphenyl] and [Ni2(CN)4(phen)2]n ( 2 ) (phen = 1,10‐phenanthroline), were synthesized and structurally characterized under solvothermal conditions. Compound 1 can be viewed as the connection of the 1D W‐type chain [Zn(trans‐bibp)] with the MoO42– anion to form a uninodal 4‐connected net, whereas 2 features one‐dimensional NiII cyanide chains decorated either with linear Ni(CN)4 side chains or with 1,10‐phenanthroline ligands bound directly to the NiII sites of the parent chain. In addition, in vitro anticancer activities of compounds 1 and 2 on four human breast cancer cells (MDA‐MB‐231, MDA‐MB‐468, SK‐BR‐3, and MCF7) was further determined.  相似文献   

6.
Different extended packing motifs of dichlorido[2‐(pyridin‐2‐yl)‐1,10‐phenanthroline]copper(II), [CuCl2(C17H11N3)], are obtained, depending on the crystallization conditions. A triclinic form, (I), is obtained from dimethylformamide–diethyl ether or methanol, whereas crystallization from dimethylformamide–water yields a monoclinic form, (II). In each case, the CuII centre is in a five‐coordinate distorted square‐pyramidal geometry. The extended packing for both forms can be described as a highly offset π‐stacking arrangement, with interlayer distances of 3.674 (3) and 3.679 (3) Å for forms (I) and (II), respectively. The reaction of diprotonated Pt(tmpip2NCN)Cl [tmpip2NCN = 2,6‐bis(2,2,6,6‐tetramethylpiperidylmethyl)benzyl] with AgPF6 under acidic conditions, followed by the addition of 2‐(pyridin‐2‐yl)‐1,10‐phenanthroline, results in a hydrogen‐bonded cocrystal, 2,2,6,6‐tetramethyl‐4‐oxopiperidinium hexafluorophosphate–2‐(pyridin‐2‐yl)‐1,10‐phenanthroline (1/1), C9H18NO+·PF6·C17H11N3, (III). The extended packing maximizes π–π interactions in a parallel face‐to‐face arrangement, with an interlayer stacking distance of 3.4960 (14) Å.  相似文献   

7.
2,5‐Dihydroxyboryl‐1,1‐dimethyl‐3,4‐bis(3‐fluorophenyl)‐silole ( 2a ) was prepared in 40% overall yield by reaction between 3‐fluorophenyl‐acetylene and dichlorodimethylsilane to yield bis[2(3‐fluorophenyl)ethynyl]dimethylsilane ( 1a ), which subsequently undergoes a reductive cyclization reaction using an excess of lithium naphthalenide. The fluoro substituted silole was applied as a co‐monomer in the Suzuki polycondensation reaction with 2,7‐dibromo‐9,9‐dioctyl‐fluorene. An oligomer ( 3a ) with a degree of polymerization of 6 was prepared and compared with an oligomer without fluoro substitution on the silole ( 3b ), with a degree of polymerization of 4. The new oligomers were spin coated onto glass slides and showed weak green photoluminescence (PL) in the solid state. Cyclic voltammetry, visible absorption spectroscopy, and density functional theory calculations showed that the fluoro substituents were sufficiently electron withdrawing to lower both the highest occupied molecular orbital and the lowest unoccupied molecular orbital in the oligomer. Two further alternating co‐oligomers were prepared from 2,5‐dihydroxyboryl‐1,1‐dimethyl‐3,4‐bis(phenyl)‐silole ( 2b ) and 1,3‐dibromo‐5‐fluoro‐benzene ( 4a ) or 1,3‐dibromobenzene ( 4b ). These oligomers both had degrees of polymerization of 8 and showed green PL in the solid state. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5116–5125, 2009  相似文献   

8.
An unusual 1D‐to‐3D transformation of a coordination polymer based on organic linkers containing highly polar push–pull π‐conjugated side chains is reported. The coordination polymers are synthesized from zinc nitrate and an organic linker, namely, 2,5‐bis{4‐[1‐(4‐nitrophenyl)pyrrolidin‐2‐yl]butoxy}terephthalic acid, which possesses highly polar (4‐nitrophenyl)pyrrolidine groups, with high dipole moments of about 7 D. The coordination polymers exhibit an unusual transformation from a soluble, solvent‐stabilized 1D coordination polymer into an insoluble, metal–organic framework (MOF)‐like 3D coordination polymer. The coordination polymer exhibits good film‐forming ability, and the MOF‐like films are insoluble in conventional organic solvents.  相似文献   

9.
The X‐ray structure analysis of the title compound, chloro[1‐cyclopropyl‐6‐fluoro‐1,4‐dihydro‐4‐oxo‐7‐(piperazin‐4‐ium‐1‐yl)‐3‐quinolinecarboxylate‐κ2O3,O4](1,10‐phenanthroline‐κ2N,N′)copper chloride dihydrate, [CuCl(C17H18FN3O3)(C12H8N2)]Cl·2H2O or [CuCl(cfH)(phen)]Cl·2H2O, where cfH is 1‐cyclopropyl‐6‐fluoro‐1,4‐dihydro‐4‐oxo‐7‐(piperazin‐4‐ium‐1‐yl)‐3‐quinolinecarboxylate and phen is 1,10‐phenanthroline, shows that the geometry around the Cu ion is a slightly distorted square pyramid. Two O atoms of the carbonyl and carboxyl groups of ciprofloxacin and two N atoms of 1,10‐phenanthroline are coordinated to the metal centre in the equatorial plane, and a Cl ion is coordinated at the apical position. Extensive intermolecular hydrogen bonding produces a supramolecular structure that consists of alternating six‐ and 12‐membered rings.  相似文献   

10.
A series of α,ω‐heterodifunctional monomers with styrene (St) and maleimide moieties bridged by a varied length of oligo‐ethylene glycol (OEG) linkers were synthesized. Cyclopolymerizations of these monomers through reversible addition–fragmentation chain transfer‐mediated alternating radical copolymerization between intramolecular St and maleimide moieties were investigated. For the monomers with three or more ethylene glycol (EG) units, their cyclopolymerizations can be realized properly in low monomer feeding concentrations, affording well‐defined cyclopolymers with crown ether encircled in their main chains. Importantly, the cyclopolymerizations of monomers with six or seven EG units in the presence of KPF6 could be enhanced by the supramolecular effects between the OEG linkers and the potassium metal ion. Thus, the monomer feeding concentration could be largely improved, which may benefit preparation of the cyclopolymers with high degrees of copolymerization. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 330–338  相似文献   

11.
Using molecular dynamics simulations we study blends of oligomers of 2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene, BTTT, and fullerene derivative based acceptors to understand the role of oligomer length and alkyl side chain (SC) length on the morphology of their blends. We use a validated coarse‐grained model of BTTT and fullerene derivatives presented in recent work along with direct comparison of morphology between simulations and experiments. In this article, we predict computationally that short alkyl SCs (6 alkyl groups) decrease the propensity of fullerene derivative acceptors to intercalate between SCs on the BTTT backbone compared to longer alkyl SCs (9 or 12 alkyl groups), and as a result increase acceptor aggregation. The decreasing acceptor intercalation and increasing acceptor aggregation do not significantly impact the positional or orientational order of the BTTT backbones. However, the BTTT oligomer backbones order better with increasing SC length in both neat systems and in blends, with the blends exhibiting higher positional order than neat systems. While these qualitative trends are similar both in 2mer blends and 4mer blends, we see a larger extent of acceptor intercalation and as a result, smaller acceptor cluster sizes in the 4mer blends. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 89–97  相似文献   

12.
The title complex [Dy(p‐ClBA)3Phen]2·2H2O was synthesized, where p‐ClBA is p‐chlorobenzoate and Phen is 1,10‐phenanthroline. The complex was characterized by various techniques including elemental analysis, IR, XRD, and molar conductance. The thermal decomposition of the complex was studied under the nonisothermal condition by TG‐DTG and IR techniques. The kinetic parameters of dehydration process were obtained from the analysis of DSC curves of the complex by the NL‐DIF and Popescu methods, respectively. © 2007 Wiley Periodicals, Inc. 40: 66–72, 2008  相似文献   

13.
In each of the zinc(II) complexes bis(acetylacetonato‐κ2O,O′)(1,10‐phenanthroline‐κ2N,N′)zinc(II), [Zn(C5H7O2)2(C12H8N2)], (I), and bis(acetylacetonato‐κ2O,O′)(2,2′‐bipyridine‐κ2N,N′)zinc(II), [Zn(C5H7O2)2(C10H8N2)], (II), the metal center has a distorted octahedral coordination geometry. Compound (I) has crystallographically imposed twofold symmetry, with Z′ = 0.5. The presence of a rigid phenanthroline group precludes intramolecular hydrogen bonding, whereas the rather flexible bipyridyl ligand is twisted to form an intramolecular C—H...O interaction [the chelated bipyridyl ligand is nonplanar, with the pyridyl rings inclined at an angle of 13.4 (1)°]. The two metal complexes are linked by dissimilar C—H...O interactions into one‐dimensional chains. The present study demonstrates the distinct effects of two commonly used ligands, viz. 1,10‐phenanthroline and 2,2′‐bipyridine, on the structures of metal complexes and their assembly.  相似文献   

14.
Two comb‐like copolymers (BIMT and PMB) composed of N‐2‐thiazolylmethacrylamide (NTMA) and 2‐(1‐butylimidazolium‐3‐yl) ethyl methacrylate tetrafluoroborate (BIMA) were prepared by free radical polymerization and reversible addition‐fragmentation chain transfer (RAFT) polymerization. The conversion of the monomers to copolymer has been confirmed by FTIR spectra and 1H NMR spectra. The metal (Ni2+, Nd3+) complexes of these two copolymers were prepared, and the magnetic behaviors of the complexes were studied. The coordinated complexes display three possible chelating structures, which lie on the nitrogen donor and oxygen donor ligands and the kinds of the metal ions. The bimetallic complexes (BIMT‐Nd‐Ni and PMB‐Nd‐Ni) were synthesized by using the different coordination sites of the polymers. The magnetic properties of the complexes show that different structures arising from the different preparations, the kinds and the contents of metal ions, and the state of the complexes can infect the exchange interaction between the metal ions and induce various magnetic phenomena. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5123–5132, 2008  相似文献   

15.
3‐Dodecylthiophene end‐capped two monomers: 2,8‐bis‐(4‐dodecyl‐thiophen‐2‐yl)‐dibenzothiophene (DBT‐3DTh) and 2,8‐bis‐(4‐dodecyl‐thiophen‐2‐yl)‐dibenzofuran (DBF‐3DTh) were synthesized via Stille coupling reaction. Both monomers exhibited emission peaks at about 400 nm with fluorescence quantum yields ranging from 0.16 to 0.21. The corresponding electroactive polymers poly(2,8‐bis‐(4‐dodecyl‐thiophen‐2‐yl)‐dibenzothiophene) (PDBT‐3DTh) and poly(2,8‐bis‐(4‐dodecyl‐thiophen‐2‐yl)‐dibenzofuran) (PDBF‐3DTh) were obtained by electropolymerization method and displayed good electrochemical stability. Both polymers switched between light gray in the neutral state and blue in the oxidized state. Kinetic investigations showed that PDBT‐3DTh exhibited a maximum optical contrast (ΔT %) of 25.23% at 575 nm with the coloration efficiency (CE) of 196 cm2 C?1. However, the electrochromic properties of PDBF‐3DTh were inferior to PDBT‐3DTh. Further detailed discussions with EDOT and 3‐alkylthiophenes end‐capped DBT/DBF hybrid electrochromic polymers were comparatively studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1468–1478  相似文献   

16.
Aromatic moieties of benzene and pyridine as side chains for poly(thiophene‐3‐yl‐amine) are rationally designed and synthesized by facile self acid‐assisted polycondensation (SAAP). Nitrogen atom is the key atom to form ammonium cation which guarantees SAAP success while other aromatic moieties are chosen carefully to attach on N atom to functionalize poly(thiophene‐3‐yl‐amine) matrix. Our results indicate that thiophene‐3‐yl‐amine is an excellent platform to construct plenty of functionalized monomers candidates for SAAP. Our study would push SAAP or AAP scope forward and pave the way to explore much more polythiophene derivatives. Furthermore, DFT calculation is carried out to deep understand AAP mechanism. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 4003–4012  相似文献   

17.
We introduce a simple method to create nanosized, ordered, and highly luminescent thin film of Eu (III)–block copolymer complex. Micelles of polystyrene–block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) in P4VP‐selective solvents (ethanol/N,N‐dimethylformamide (DMF) mixture) serve as nanoreactors for the synthesis of Eu(III)–block copolymer complex with the presence of 1,10‐phenanthroline (Phen) as cooperative ligand. The resulted quaternary complexes were characterized by FT‐IR spectra, 15N NMR spectra, and elemental analysis, indicative of a composition of Eu(III)–(PS‐b‐P4VP)–Phen–5DMF. Atomic force microscopy and transmission electron microscopy investigations reveal that the Eu(III)–(PS‐b‐P4VP)–Phen–5DMF complex can self‐organize into hexagonally ordered thin films when dip‐coated from the solution onto silicon or silica glass substrates. Such ordered thin films can emit red fluorescence of Eu3+ with strong intensity and long lifetime. This method can be easily extended to prepare other ordered luminescent rare earth–polymer complexes thin films. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2181–2189, 2005  相似文献   

18.
Ligands based on polycarboxylic acids are excellent building blocks for the construction of coordination polymers; they may bind to a variety of metal ions and form clusters, as well as extended chain or network structures. Among these building blocks, biphenyltetracarboxylic acids (H4bpta) with C 2 symmetry have recently attracted attention because of their variable bridging and multidentate chelating modes. The new luminescent three‐dimensional coordination polymer poly[(μ5‐1,1′‐biphenyl‐2,2′,4,4′‐tetracarboxylato)bis[μ2‐1,4‐bis(1H‐imidazol‐1‐yl)benzene]dizinc(II)], [Zn2(C16H6O8)(C12H10N4)]n , was synthesized solvothermally and characterized by single‐crystal X‐ray diffraction, elemental analysis and IR spectroscopy. The crystal structure contains two crystallographically independent ZnII cations. Both metal cations are located on twofold axes and display distorted tetrahedral coordination geometries. Neighbouring ZnII centres are bridged by carboxylate groups in the syn anti mode to form one‐dimensional chains. Adjacent chains are linked through 1,1′‐biphenyl‐2,2′,4,4′‐tetracarboxylate and 1,4‐bis(1H‐imidazol‐1‐yl)benzene ligands to form a three‐dimensional network. In the solid state, the compound exhibits blue photoluminescence and represents a promising candidate for a thermally stable and solvent‐resistant blue fluorescent material.  相似文献   

19.
《中国化学会会志》2017,64(12):1478-1495
In this work, mixed ligand complexes derived from ethyl 2‐(2‐hydroxybenzylidine)‐hydrazine carboxylate (HL) and 1,10‐phenanthroline (Phen) as ligands were synthesized and their structures elucidated by elemental analysis, infrared (IR), electronic,1H NMR, and mass spectra, X‐ray diffraction (XRD), magnetic susceptibility measurements, and TG/DTG analyses. The analytical and spectral data support the formation of the complexes with the central ion in each complex six‐coordinated and a slightly distorted octahedral geometry. The IR spectra showed that HL and Phen ligands act as neutral bidentates. The XRD patterns of the complexes showed their crystalline nature. The calculated bond length and the force constant F (U═O) in the uranyl complex are 1.738 Å and 685.90 Nm−1, respectively. The molar conductance values of the synthetic complexes in DMF were found to be in the range 5.00–274.06 S cm2/mol at room temperature. The thermodynamic parameters were evaluated by using the Coats–Redfern (CR) and Horowitz–Metzeger (HM) methods. Theoretical molecular structures were investigated by the density functional theory/B3LYP method using the Gaussian 98 W basis set. The nematicidal activity of the ligands and its metal complexes was also studied.  相似文献   

20.
The new asymmetrical organic ligand 2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole ( L , C17H13N5O), containing pyridine and imidazole terminal groups, as well as potential oxdiazole coordination sites, was designed and synthesized. The coordination chemistry of L with soft AgI, CuI and CdII metal ions was investigated and three new coordination polymers (CPs), namely, catena‐poly[[silver(I)‐μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole] hexafluoridophosphate], {[Ag( L )]PF6}n, catena‐poly[[copper(I)‐di‐μ‐iodido‐copper(I)‐bis(μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole)] 1,4‐dioxane monosolvate], {[Cu2I2( L )2]·C4H8O2}n, and catena‐poly[[[dinitratocopper(II)]‐bis(μ‐2‐{4‐[(1H‐imidazol‐1‐yl)methyl]phenyl}‐5‐(pyridin‐4‐yl)‐1,3,4‐oxadiazole)]–methanol–water (1/1/0.65)], {[Cd( L )2(NO3)2]·2CH4O·0.65H2O}n, were obtained. The experimental results show that ligand L coordinates easily with linear AgI, tetrahedral CuI and octahedral CdII metal atoms to form one‐dimensional polymeric structures. The intermediate oxadiazole ring does not participate in the coordination interactions with the metal ions. In all three CPs, weak π–π interactions between the nearly coplanar pyridine, oxadiazole and benzene rings play an important role in the packing of the polymeric chains.  相似文献   

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