Two d10 coordination polymers based on 4,4′-(hexafluoroisopropylidene)diphthalic acid: Syntheses,structures and physical properties

Two novel coordination polymers, [Zn₂(FA)(4,4′-bipy)₂]·2H₂O (1) and Cd₂(FA)(2,2′-bipy) (2), (H₄FA = 4,4′-(hexafluoroisopropylidene)diphthalic acid, 4,4′-bipy = 4,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine), have been synthesized under hydrothermal conditions, and their structures were determined by single-crystal X-ray diffraction. Polymer 1 features an unusual three-dimensional (3D) network with (4 · 6² · 8³)(4² · 6² · 8²) topology. Polymer 2 has a complicated 3D framework and crystallizes in non-centrosymmetric space group (Fdd2) belonging to polar point group (C_2v), which displays a strong SHG response and ferroelectric properties. Moreover, the luminescent properties of 1 and 2 have also been investigated.     

Three rare Ln–Na heterometallic 3D polymers based on sulfate anion: Syntheses,structures, and luminescence properties

Three Ln–Na heterometallic 3D polymers based on sulfate anion, [LnNa(SO₄)₂(H₂O)] (Ln = Gd (1); Tb (2); Dy (3)), were synthesized under hydrothermal conditions, which are the first examples of Ln–Na sulfates. These compounds crystallize in the trigonal P3₁21 space group, and display a 6-connected sma topological structure with a Schäfli symbol of (4¹⁰·6⁵). The characteristic analyses reveal that compounds 1–3 display excellent thermal stability, and all exhibit antiferromagnetic interactions between the metal centers. The luminescent properties of 2 and 3 show the characteristic terbium and dysprosium luminescence. The strong luminescence in the green light (⁵D₄ → ⁷F₅) region for 2 and blue light (⁴F_9/2 → ⁶H_15/2) region for 3 indicate that they may be excellent candidates for green or blue fluorescent materials.     

Effects of 3,4′-oxydianiline on the structures and properties of a novel aromatic polyimide foam

Aiming at the low volumetric shrinkage, a novel aromatic polyimide foam is successfully prepared from polymethane polyphenyl isocyanate (PAPI) and a poly(amic-acid) precursor which has been synthesized from 3,4′-oxydianiline (3,4′-ODA) and pyromellitic dianhydride (PMDA). In this research, five polyimide foams, with different contents of 3,4′-ODA, are comparatively studied including structural, thermal, mechanical, shrink, and degradation properties. The results indicate that the content of 3,4′-ODA has minor influence on chemical structures, but significant influence on cell structures of the foams. With the increase of 3,4′-ODA, the volumetric shrinkages, apparent densities and the compressive and flatwise tensile strengths of the materials decrease. The glass transition temperatures (T_g) decrease from 301°C to 279°C, and the 5% weight loss temperatures (T_5%) increase from 323°C to 340°C. Through TG-FTIR analysis, we can observe that the addition of 3,4′-ODA has no influence on the pyrolysis mechanism of polyimide foams. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

New assembly of transition metal complexes based on [GeW9O34]10− building blocks: Syntheses,crystal structures and magnetic properties

Two new polyoxotungstates Na₃H(C₃H₅N₂)₄[{Cu(C₃N₂H₄)₂}₂Cu₄(H₂O)₂(GeW₉ O₃₄)₂]·27H₂O (1) and Na₁₀H₈[Mn₆Ge₃W₂₄O₉₄(H₂O)₂]·37H₂O (2) have been synthesized in aqueous solution. The polyoxoanion frameworks of the two compounds are built on the lacunary Keggin-type polyanion [GeW₉O₃₄]^10?. The structure of compound 1 is a Weakley-type species capped by two [Cu(C₃N₂H₄)₂]²⁺ units through four bridging oxygen atoms on two opposite W₄O₄ faces. Compound 2 is a banana-shaped polyoxometalate consisting of two tri-Mn substituted [Mn₃GeW₉O₃₄]^4? Keggin units and a hexavacant bridging cluster [GeW₆O₂₆]^12?. The magnetic investigations demonstrate the presence of both antiferromagnetic and ferromagnetic exchange interactions for 1 and weak antiferromagnetic interactions for 2.     

Novel D-π-A system based on zinc porphyrin dyes for dye-sensitized solar cells: Synthesis, electrochemical, and photovoltaic properties

We have designed and synthesized novel zinc porphyrin dyes which have a D-π-A system based on porphyrin derivatives containing a triphenylamine (TPA) electron-donating group and a phenyl carboxyl anchoring group substituted at the meso position of the porphyrin ring, yielding the push-pull porphyrins as the most efficient green dye for dye-sensitized solar cell (DSSC) applications. The synthesis and characterization of a novel D-π-A system based on zinc-porphyrin derivatives have been investigated through their photophysical and photoelectrochemical studies. A large red-shift of the absorption maxima due to introduction of the TPA moiety at the meso position of the porphyrin ring was expected in the D-π-A porphyrins, but the absorption maxima of HKK-Por dyes were a little red-shifted in contrast to Zn[5,-10,15-triphenyl-20-(4-carboxylphenyl)-porphyrin], due to the tilted structure between TPA and the porphyrin unit. Under the photovoltaic performance measurement, the maximum incident photon-to-current conversion efficiency (IPCE) value of the DSSC based on HKK-Por 5 was slightly higher than the efficiencies of the DSSCs based on other HKK-Por dyes due to the introduction of the alkoxy group into the TPA moiety at the meso position of the porphyrin ring. A maximum photon-to-electron conversion efficiency of 3.36% was achieved with the DSSC based on HKK-Por 5 dye (J_SC = 9.04 mA/cm², V_OC = 0.57 V, FF = 0.66) under AM1.5 irradiation (100 m Wcm⁻²).     

Synthesis and properties of novel donor–acceptor copolymers based on thiophene and squaraine moieties

Two novel donor–acceptor copolymers were synthesized by Sonogashira cross-coupling of alkyl/alkoxy thiophene and dibromo-substituted squaraine moieties. The structures and properties of these polymers were characterized using FT–IR, NMR, UV–Vis, gel permeation chromatography, and cyclic voltammetry. Both copolymers are readily soluble in common organic solvents. The polymer films exhibit broad absorption in the wavelength range from 300 to 1000 nm with the maximum peaks over 750 nm. Electrochemical studies reveal that the band gaps of the polymers range from 1.05 to 1.36 eV. Compared to the alkyl thiophene, the alkoxy thiophene units can effectively lower the band gap and result in significant red-shift absorption spectrum of the resulted polymer. The strong overlap of the solar spectrum and the extremely low band gaps of the polymers suggest that they may be promising candidates for solar cells.     

Syntheses and structures of cadmium(II) and cobalt(II) coordination polymers based on 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-imidazole) and carboxylate ligands

Two novel coordination polymers containing Cd(II) and Co(II) metals, connected via 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-imidazole) (L) ligand, have been synthesized. Compound [Cd(L)₂(p-BDC)] · 2H₂O (1) (p-BDC = 1,4-benzenedicarboxylate anion) is a three-dimensional interdigitated supramolecular architecture. Compound [Co(L)(BTCA)_0.5] (2) (BTCA = 1,2,3,4-butanetetracarboxylate anion) possesses a unique (3,4)-connected 3D framework with (8³)₂(8⁵ · 10) topology.     

Curing behavior,thermal, and mechanical properties of epoxy/polyamic acid based on 4,4′-biphtalic dianhydride and 3,3′-dihydroxybenzidine

Different synthesis routes were studied to obtain 4,4′-biphtalic dianhydride/3,3′-dihydroxybenzidine polyimide precursors (polyamic acids [PAAs]) with different inherent viscosities (IVs) and imidization degrees. The synthesized PAAs were introduced as a thermoplastic modifier into an epoxy (EP) resin. Different loadings of PAA were used to investigate the curing behavior, heat resistance, and mechanical properties. The onset curing temperature of the EP by adding 20 wt% PAA diminished by around 15°C. Thermogravimetric analysis revealed that the initial and 10 wt% weight loss temperature for EP with 5 wt% PAA improved by 13°C and 7.7%, respectively. Further, the results of tensile and plane-strain fracture toughness tests indicated that as the amount of PAA increased, the strength and toughness of EP decreased. These improvements were due to the high heat resistance and mechanical properties of PI precursor introduced into the EP, which formed a three-dimensional structure together. The interlaminar shear strength (ILSS) of the system experienced a reduction; however, after adding 2 phr nanosilica to the system containing PAA with average IV and imidization degree, ILSS showed 4.4% increment.     

Two Novel Bimetallic Cyano-Bridged Coordination Polymers Containing the 2,2′-(Ethylenedioxy)bis (Ethylamine): Syntheses,Structural, Thermal and Magnetic Properties

Two new cyano bridged bimetallic polymeric complexes, [Ni(edbea)Ni(CN)₄]·1/2H₂O (1) and [Cu(μ-edbea)(μ-CN)₂ Ni(CN)₂]·H₂O (2) [edbea = 2,2′-(ethylenedioxy)bis(ethylamine)] have been synthesized by adding metal chloride (M = Ni^II and Cu^II), and edbea into [Ni(CN)₄]²⁻ in water–ethanol solution and then characterized by elemental analysis, infrared (IR) and electron paramagnetic resonance (EPR) (for only complex 2) spectra, variable temperature magnetic measurement, and thermal gravimetric analysis. The X-ray diffraction crystal structure of complex 2 shows a 2D polymeric chain –edbea(N5,O1)–Cu1–N1C1–Ni(CN)2–C4N6–Cu1–(N6,O2) edbea– in which the Cu^II centers are linked by two cyano and one edbea. The powder EPR spectrum of the complex 2 has shown that Cu^II ions are located in rhombically distorted octahedral sites. The magnetic properties of the coordination polymers have been studied in temperature range of 15–300 K. The magnetic behaviors investigation of complexes 1 and 2 indicated the presence of a very weak antiferromagnetic interaction.     

New dinuclear lanthanide(III) complexes based on 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and 2,2′-bipyrimidine

Reaction of mononuclear Ln(fod)₃ chelates (where fod is the anion of 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and Ln = Nd, Eu, Tb and Lu) with potentially bridging ligand 2,2′-bipyrimidine (bpm) in 2:1 mole ratio in ethanol afforded new dinuclear lanthanide complexes of the form [Ln(fod)₃-(μ-bpm)-Ln(fod)₃]. Neodymium complex is one of the rare bipyrimidine-bridged dinuclear complexes. The absorption spectrum of the neodymium complex displays characteristic hypersensitive as well as non-hypersensitive transitions. The excitation of Eu–Eu and Tb–Tb complexes at 355 nm produces an intense red and green luminescence, respectively.     

Sulfonated polyimide copolymers based on 4,4′-diaminostilbene-2,2′-disulfonic acid and 3,5,3′,5′-tetramethylbenzidine with enhanced solubility

A new series of six-membered ring sulfonated polyimides with different combinations of two comonomers in the nonsulfonated diamine was prepared by one-step high-temperature polycondensation in m-cresol to improve the solubility of the resulting sulfonated polyimides. They are based on 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4′-diaminostilbene-2,2-disulfonic acid sulfonated diamine, and equimolar mixture of 3,5,3′,5′-tetramethylbenzidine (TMB) and 4,4′-oxydianiline, bis(4-aminophenyl)methane, or bis(4-(aminophenoxy)-4-phenyl)isopropylidene nonsulfonated diamines. The introduction of TMB comonomer in the nonsulfonated diamine resulted in a remarkable improvement in the solubility of the resulting polyimides in comparison with the corresponding single-monomer nonsulfonated diamine polyimides. Flexible, transparent, and tough membranes were prepared by solution casting method from the different polyimides. The membranes were characterized with FTIR and ¹H-NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, water uptake, and ion-exchange capacity measurements. They exhibit high thermal stability and good correlation between the ion-exchange capacity and water uptake values.     

A novel chromo- and fluorogenic dual responding H2PO4− receptor based on an azo derivative

A simple, novel anion receptor based on 4-hydroxy-3-(N-phenyl-thiourea-N′-nitrilo-methylidynyl)-azobenzene with hybrid –OH and thiourea binding sites was synthesized and characterized. Anion binding character was determined using visual inspection, UV–vis, fluorescence and ¹H NMR analyses. The addition of F^?, AcO^? and H₂PO₄^? resulted in a marked red shift of the charge-transfer absorbance band (Δλ = 140 nm, from 340 nm to 480 nm) accompanied by a color change from light yellow to orange.     

Two novel cadmium(II) coordination polymers based on bis-functionalized ligand 4′-(4-carboxyphenyl)-2, 2′:6′, 2″-terpyridine

Two novel cadmium(II) coordination polymers [Cd(cptpy)₂]_n·nH₂O (1) with a 1D double chain structure and [Cd₂(cptpy)₂(ox)]_n·2.5nH₂O (2) with an interesting 3-connected uninodal six-fold interpenetrating ths network (Hcptpy = 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine, H₂ox = oxalic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, single crystal X-ray diffraction and fluorescence spectra.     

Syntheses,structures and photoluminescence of Ln(III)–Cu(I) coordination polymers based on benzimidazole-5-carboxylate and oxalate ligands

Three novel Ln(III)–Cu(I) coordination polymers, namely [LnCu(Hbic)₃(ox)_0.5] [Ln = Sm (1), Dy (2), Hbic = benzimidazole-5-carboxylate, ox = oxalate] and [EuCu(Hbic)₂(ox)H₂O]·2H₂O (3) have been hydrothermally synthesized and stucturally characterized. Both complexes 1 and 2 display the same unusual 2D layer heterometallic coordination frameworks that are built up by dimeric [Ln₂(Hbic)₆] cores and oxalate ligands by sharing Cu(I) ions. Complex 3 represents 1D polymeric chain architecture constructed from Eu₂Cu₂ ring units and oxalate ligands. Furthermore, the luminescent property of complex 3 has also been investigated.     

Synthesis and photoluminescent properties of four novel trinuclear europium complexes based on two tris-β-diketones ligands

Four novel trinuclear europium complexes with two tris-β-diketones ligands have been synthesized, and the chemical structures of ligands and complexes were characterized by FT-IR, UV-vis, ¹H NMR, ¹³C NMR, XRD, ESI-MS, and element analysis. The potoluminescent properties of trinuclear complexes in solid and THF solution were investigated. All trinuclear complexes exhibited strong relative luminescent intensity and long luminescent lifetime. Meanwhile, the results of lifetime decay curves indicated that only one chemical environment existed around the europium ion. The intrinsic luminescent quantum yields (Φ_LN) and experimental intensity parameters of trinuclear complexes were obtained based on the emission spectra and luminescent lifetime of ⁵D₀ excited state for europium ion. All trinuclear europium complexes exhibited relative high intrinsic luminescent yield and intensity parameters. Especially, due to the contribution of addition two europium lumophors in trinuclear europium complexes, the trinuclear complexes containing TTA exhibited much longer lifetime and higher intrinsic quantum yield than mononuclear europium complex Eu(TTA)₃phen.     

Synthesis,characterization and third-order nonlinear optical properties of novel hyperbranched donor–acceptor polyfluorenes based on 1,3,6,8-tertsubstituted carbazole core

Two novel hyperbranched donor–acceptor polyfluorenes based on 1,3,6,8-tertsubstituted carbazole core (4BrCzP1 and 4BrCzP2) were synthesized and characterized. The third order nonlinear optical properties of the materials were studied using Z-scan technique with femtosecond Ti: sapphire laser with delivering pulses of 140 fs at 800 nm. The nonlinear optical refractive index was 9.29 × 10^?8 esu for 4BrCzP1 and 3.19 × 10^?7 esu for 4BrCzP2, respectively. While the third order nonlinear susceptibility was 1.29 × 10^?9 esu for 4BrCzP1 and 4.33 × 10^?9 esu for 4BrCzP2, respectively. The experimental results indicated that the hyperbranched polyfluorenes was a promising candidate in the application of third order nonlinear optical materials.     

Spin canting in a novel (3,4)-connected mixed-valence cobalt coordination polymer based on oxalates and [Co(Hbiim)3] (H2biim = 2,2′-biimidazole) building blocks

Hydrothermal treatment of cobalt chloride, 2,2′-biimidazole (H₂biim), oxalate acid and NaOH at 160 °C for five days produced a three-dimensional mixed-valence metal-organic framework [Co^III(Hbiim)₃]₂[Co^II₃(ox)₃]·4H₂O (1). Compound 1 exhibits a 3D network with tri-nodal (3-c)₂(4-c)₃ topology, in which [Co^III(Hbiim)₃] building blocks as 3-connected nodes, and Co^II ions as 4-connected nodes. The magnetic measurements reveal that compound 1 exhibits a spin canting antiferromagnetic coupling between adjacent Co^II ions.     

Synthesis,crystal structure and luminescent properties of new tris-β-diketonate Eu(III) complex with thiadiazolophenanthroline derivative ligand

Herein we describe the synthesis, characterization and spectroscopic properties of the complex tris-(thenoyltrifluoroacetonate)([1, 2, 5]thiadiazolo[3, 4-f][1,10]phenanthroline) europium(III) acetonitrile solvate, [Eu(TTA)₃ TDPHEN] 1.5CH₃CN, where TTA = 2-thenoyl trifluoroacetone and TDPHEN = [1, 2, 5]thiadiazolo[3, 4-f][1, 10] phenanthroline. X-ray crystallography reveals that it is an eight-coordinate Eu(III) complex containing three β-diketonate chelates and one N,N′-bidentate ligand, [1, 2, 5] thiadiazolo[3, 4-f][1, 10] phenanthroline. The excitation at 340 nm of the europium complex in a solution of acetonitrile, and at room-temperature, showed the typical Eu(III) red emission as a sharp band at 611 nm, characteristic of Eu(III) due to the transition ⁵D₀ → ⁷F₂. This complex also showed red emission in the solid state phase (λ_em = 612 nm).     

A novel injectable and in situ crosslinked hydrogel based on hyaluronic acid and α,β-polyaspartylhydrazide

A new injectable and in situ crosslinked hydrogel, based on a hyaluronic acid (HA) derivative and α,β-polyaspartylhydrazide (PAHy), was produced during the research. This biodegradable and high molecular weight hydrogel can be in situ crosslinked in 15 s by the condensation reaction between aldehyde and amine groups. The HA derivative carrying aldehyde (HAALD) was oxidized from HA by sodium periodate, while the synthesis of hydrogel was performed in a phosphate-buffered saline solution (PBS) using HAALD and PAHy without addition of crosslinker or catalyst. The pH and concentration of the reaction solution, considered as the important factors of the amine-aldehyde reaction, were changed to reveal the crosslinking rule. Thereafter, crosslinked hydrogels were characterized by gelation time, gel content, swelling ratio, and in vitro degradation. Furthermore, the modified polymers were characterized by Fourier transformed infrared (FTIR) spectroscopy to examine their structures. Results from scanning electron microscope (SEM) observations confirmed that a freeze-dried sample revealed a porous hydrogel structure with interconnected pores. The measurement of the cell adhesion confirmed the application potential of HAALD-PAHy hydrogels. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Syntheses and Characterization of Two New M(II)-5,5′-dimethyl-2,2′-bipyridine (M = Cd and Pb) Coordination Polymers and Study of Their Thermal and Electrochemical Properties

Two new cadmium(II) and lead(II)-thiocyanato coordination polymers with 5,5′-dimethyl-2,2′-bipyridine (5,5′-dm-2,2′-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and ¹H NMR spectroscopy and by X-ray crystallography. Thermal and electrochemical properties were also studied as well. These complexes have formed formula [Cd(5,5′-dm-2,2′-bpy)(NCS)₂]_n (1) and [Pb(5,5′-dm-2,2′-bpy)(CH₃COO)(NCS)]_n (2). The coordination numbers of Cd^II in 1 and Pb^II in 2 are six (CdN₄S₂) and seven (PbN₃O₃S₂), respectively. In 2, “stereo-chemically active” electron lone pairs and the coordination spheres were hemidirected. Bridging properties of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.