Novel 5-benzazolyl-10,15,20-triphenylporphyrins and β,meso-benzoxazolyl-bridged porphyrin dyads: Synthesis, characterization and photophysical properties

Novel 5-benzazolyl-10,15,20-triphenylporphyrins and β,meso-benzoxazole-linked diporphyrins were synthesized through La(OTf)₃ catalyzed reaction of newly prepared 5-(3,4-diaminophenyl)-10,15,20-triphenylporphyrin or 5-(3-amino-4-hydroxyphenyl)-10,15,20-triphenylporphyrin with aromatic aldehydes in 1,2-dichlorobenzene. On metalation with zinc acetate, freebase β,meso-benzoxazole-linked diporphyrin was successfully converted to the Zn-Zn diporphyrin complex in good yield. The synthesized porphyrin analogues were characterized using electronic absorption, IR and ¹H NMR spectroscopy in addition to mass and elemental analyses. The fluorescence studies of 5-benzazolyl-10,15,20-triphenylporphyrins showed efficient intramolecular energy transfer from the pyrene and fluorene subunits to the porphyrin core. In addition, the fluorescence quenching observed in β,meso-benzoxazolyl-bridged porphyrin dyads was attributed to the possible nonplanarity of a component of the diporphyrins. The freebase-Ni diporphyrin complex underwent strong emission quenching in comparison to that of freebase diporphyrin and dizinc diporphyrin analogues.     

Synthesis and optical properties of three novel functional polyurethanes bearing nonlinear optical chromophoric pendants with different π electron conjugation bridge structure

High molecular weight functional polyurethanes bearing large π electron conjugated chromophoric pendants with different conjugation bridge structure, poly(1a), poly(1b), and poly(1c), were synthesized and characterized by FTIR, ¹H NMR and UV-vis absorption spectra. Their optical properties were evaluated by optical limiting and nonlinear optical analyses. The results show that these polymers possess good optical limiting and large nonlinear optical properties, which are attributed to the long D-π-A conjugated π electron structure of the NLO-chromophoric segment. Poly(1a) with CC double bond as π electron conjugation bridge shows better optical limiting property than poly(1b) and poly(1c) with CN or NN double bond as conjugation bridge structure under the same linear transmittance, while poly(1c) with NN double bond as π electron conjugation bridge of the NLO-chromophoric segment is superior on nonlinear optical properties to poly(1a) and poly(1b) with CC and CN double bonds as π electron conjugation bridge structure, respectively.     

Synthesis and photovoltaic properties of D-π-A copolymers based on thieno[3,2-b]thiophene bridge unit

Three D-π-A copolymers containing thieno[3,2-b]thiophene (TT) bridge and BDT, carbazole, fluorene as D units and benzothiadiazole as A unit were synthesized and characterized. These copolymers of PBDT-tt-BT, PC-tt-BT and PF-tt-BT exhibited enough high thermal stabilites and good solubilites in chloroform and dichlorobenzene. Among the copolymers, with the increase of the electron-donating abilities of the D units from fluorene to carbazole further to BDT, the absorption spectra of PF-tt-BT shows blue shift and that of PBDT-tt-BT shows red shift comparing to that of PC-tt-BT in their solutions and films. Meanwhile, by electrochemical cyclic voltammetry measurements we found the HOMO levels vary in the same trench according to their electron-donating abilities. Under the illumination of AM 1.5G, 100 mW/cm², power conversion efficiency (PCE) of the PSCs based on these copolymers as donors and PC₇₀BM as acceptor were measured and PBDT-tt-BT shows a higher efficiency of 4.91% than PC-tt-BT and PF-tt-BT based devices mostly due to its higher hole mobility and broader absorption range. These results indicate that PBDT-tt-BT is a promising photovoltaic polymer donor material for efficient PSCs.     

Synthesis of new N, N-diphenylhydrazone dyes for solar cells: Effects of thiophene-derived π-conjugated bridge

Four novel D-π-A hydrazone dyes (HT, HM, HE, and HO) with an N, N-diphenylhydrazone moiety as the electron donor, different thiophene-derived π-conjugated bridges and a cyanoacrylic acid moiety as the electron acceptor have been designed and synthesized for the application in dye-sensitized solar cells. The influences of thiophene-derived bridges on the photoelectrochemical and photovoltaic performance of these hydrazone dyes were investigated. Results demonstrate that the introduction of 3,4-dialkyloxythiophene could red-shift the dye’s absorption spectrum due to the enhancement of the electron-donating ability of π-conjugated bridges. Importantly, electrochemical impedance spectroscopy analysis reveal that 3,4-dialkyloxythiophene bridge could change the charge recombination resistance at the TiO₂/dye/electrolyte interface and as a result to improve the open-circuit photovoltage. Among the four dyes, HO exhibits the maximum power conversion efficiency of 5.83% (V_oc = 0.65 V, J_sc = 12.69 mA/cm², FF = 0.707) under simulated AM 1.5 irradiation (100 mW/cm²).     

Push–pull chromophores comprising benzothiazolium acceptor and thiophene auxiliary donor moieties: Synthesis,structure, linear and quadratic non-linear optical properties

Novel, push–pull chromophores combining a cationic benzothiazolium acceptor moiety and either one or two thiophene rings as a part of the conjugated π-system between the donor and the acceptor moieties have been synthesized and characterized. The chromophores displayed pronounced quadratic NLO activity with their first molecular hyper polarizabilities in agreement with their linear spectral properties.     

A critical theoretical study on linear and nonlinear optical properties of macrocyclic thiophene derivatives with different connecting π-conjugated bridge and ring size

This contribution reports the geometries, electronic structures, linear and nonlinear optical properties of a series of macrocyclic thiophene derivatives with different connecting π-bridge and ring size in theory. It provides great optical properties that both OPA and TPA peaks shift red as Ne increases and in different window, which don't superimpose on each other, and the values of δ⁽¹⁾_max and δ⁽²⁾_max enlarge, while the largest δ⁽²⁾_max for C[6T_A_E]₃ observed at long wavelength (725.9 nm) is 23 times larger than that of the unit C[6T_A_E]. Besides connecting bridge and ring size, several key parameters essentially influencing on NLO property were highlighted, including M_0k, M_kn, ?_0k × ?_kn and Ne. In addition, ICT impacting on the values of δ⁽²⁾_max was analyzed by contour surfaces of the frontier orbitals and ΔQ of thiophene and bridge. More particularly, large negative value of Reγ indicates their self-defocusing, implying it can be applied in self-defocusing optical power limiting materials.     

Synthesis,optical and electrochemical properties of novel D-π-A type conjugated polymers based on benzo[c][1,2,5]selenadiazole unit via alkyne module

Three novel donor-π-acceptor (D-π-A) type conjugated polymers P-1, P-2, and P-3 based on benzo[c][1,2,5]selenadiazole moiety and phenyl or naphthyl group via alkyne module were firstly prepared by Sonogashira–Hagihara reaction of various diiodo aryl compounds with the key monomer 4,7-diethynylbenzo[c] [1,2,5]selenadiazole (M-1), which was synthesized by a strategy of firstly introducing the trimethylsilylacetylene flexible group, and then introducing the selenium atom. The polymers displayed obvious absorption peaks at the region from 503 to 510 nm and narrow orange-red or red fluorescence in the range of 576–595 nm because benzo[c][1,2,5]selenadiazole unit can effectively reduce the lowest unoccupied molecular orbital (LUMO) energy levels of these polymers. The band gaps of these polymers can be tuned in the range of 1.37–1.76 eV by using different aryl donor groups. These findings indicate that these benzo[c][1,2,5]selenadiazole-based conjugated polymers can be developed for excellent fluorescent materials.     

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).     

Optical properties of donor-π-(acceptor)n merocyanine dyes with dicyanovinylindane as acceptor group and triphenylamine as donor unit

Donor-π–(Acceptor)_n (D-π-A) type dyes were synthesized and their absorption and emission spectra investigated in different solvents. Strong acceptor units imparted large red-shifts in absorption; the twisting of the dye's structure imposed by an acceptor unit quenched fluorescence. Electron delocalization before and after excitation was observed according to molecular orbital calculations. The results indicated potential use of the dyes as electro-optical materials.     

New linear π-conjugated polymers via Suzuki coupling of (1Z, 3Z)-1,4-dibromo-1,4-diaryl-buta-1,3-diene with aromatic diborates: Synthesis and photophysical properties

A series of new linear π-conjugated polymers have been synthesized via Suzuki coupling of (1Z, 3Z)-1,4-dibromo-1,4-diaryl-buta-1,3-diene with aromatic diborates. The structures were characterized by NMR spectroscopy, IR spectroscopy and GPC. All of them exhibit good thermal stability with high decomposition temperature over 340 °C. It was found that the absorption and emission of the polymers can be adjusted through changing the side aromatic group, and the partial twisted structure of two aromatic groups at the end carbon of buta-1,3-diene unit can hinder the interchain interaction of conjugated main chain and improve the photophysical properties of the polymers in the solid state. The electrochemical and electroluminescent properties of the polymers were primarily studied.     

Synthesis and characterization of new imidazole and fluorene–bisphenol based polyamides: Thermal,photophysical and antibacterial properties

A new para-linked diether-diamine, 9,9-bis{4-[2-(4,5-diphenylimidazol-2-yl)-4-aminophenoxy] phenyl}fluorene (III), bearing fluorene–bisphenol and two ortho-linked diaryl-substituted imidazole rings were synthesized by the catalytic reduction of the nitro groups of compound (II), 9,9-bis{4-[2-(4,5-diphenylimidazol-2-yl)-4-nitrophenoxy]phenyl}fluorene, by using hydrazine monohydrate in the presence of Pd/C. Compound (II) was synthesized by the nucleophilic chloro displacement reaction of the synthesized 2-(2-chloro-5-nitrophenyl)-4,5-diphenyl-1H-imidazole with 9,9-bis(4-hydroxyphenyl)fluorene in refluxing DMAc in the presence of potassium carbonate. This diamine was condensed directly with aliphatic and aromatic diacids via the Yamazaki–Higashi phosphorylation method in the presence of triphenylphosphite (TPP), pyridine (Py) and halide salt to give high molecular polyamides (PAs). The synthesized PAs were obtained in quantitative yields with inherent viscosities between 0.51 and 0.76 dL g^?1. The structures of diamine and PAs were characterized by elemental analysis, FT-IR and NMR spectroscopy, and properties of PAs were investigated by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and UV–visible and fluorescence spectroscopy. The PAs showed good solubility in aprotic and polar organic solvents, with high thermal stability exhibiting the glass transition temperatures (T_gs) and 10% weight loss temperatures (T_10%) in the range of 226–330 °C and 400–466 °C in air, respectively, and fluorescence emission with maximum wavelengths (λ_em) in the range of 417–473 nm with quantum yields (Φ_f) of 9–35%. Two of these polymers together with compounds (II) and (III) were also screened for antibacterial activity against Gram positive and Gram negative bacteria.     

Aryloxy and benzyloxy compounds of hafnium: Synthesis, structural characterization and studies on solvent-free ring-opening polymerization of ε-caprolactone and δ-valerolactone

A large variety of aryloxy compounds and benzyloxy derivatives of Hf(IV) were synthesized from Hf(O-tBu)₄ using the alcoholysis route. These compounds were completely characterized using various spectroscopic and analytical methods along with single crystal X-ray diffraction studies. Multinuclear NMR studies prove high degree of fluxional behavior of these compounds in solution. They adopt a dimeric structure in the solid-state as seen from X-ray diffraction studies on a few of them. These compounds are powerful catalysts for the ring-opening polymerization of ε-caprolactone (CL) and δ-valerolactone (VL) resulting in high number average molecular weight (M_n) polymers and controlled molecular weight distributions (MWDs). Significant control in the polymerization was achieved with these compounds as initiators in comparison to their titanium and zirconium analogues. Kinetic studies reveal that the rates of such polymerizations are in general slower than the corresponding titanium and zirconium derivatives. ¹H NMR and MALDI-TOF studies of low molecular weight oligomers suggest that these polymerizations proceed by the activated monomer mechanism.     

Synthesis of Fe–Pr co-doped ZnO nanoparticles: Structural,optical and antibacterial properties

In the present work, we studied the role of Fe and Pr addition on the structural, optical and antibacterial properties of spherical ZnO nanoparticles synthesized via sol gel method. The lattice constants values increased, while the average crystallite size decreases as the Pr concentration varies from 0.00 to 0.04. The Fe and Pr cations insertion in the Wurtzite structure were also confirmed by the changes in Zn–O bond length (1.9763 Å to 1.9793 Å for 0.00 ≤ y ≤ 0.04). Raman and FTIR spectroscopies validated the ZnO single-phase formation, and the analysis suggests the existence of oxygen vacancies. The samples showed agglomerated spherical morphology and formation of nanoplate homogeneously organized, while the textural properties were affected by the Fe inclusion. All samples presented band gap values lower than expected for bulk ZnO and the lowest values were obtained for samples containing Fe and Pr. The analysis and deconvolution of photoluminescence spectra confirmed the structural defects formation, caused by the synthesis conditions used and dopants ions inclusion. The antimicrobial activity against Escherichia coli and Staphylococcus aureus using the direct contact method showed superior activity for S. aureus due to the nanoparticles-bacteria interactions. The synergistic effect of dopants may have contributed to the better performance observed against S. aureus, while the Pr concentration directly influenced the inhibitory effect of E. coli. Therefore, the synthesized materials are promising to eliminate pathogenic microorganisms.     

Synthesis, characterization and photocatalytic activity of β-Ga2O3 nanostructures

Nanostructured β-Ga₂O₃ samples were prepared by a combination of the solvothermal processes and subsequent heat treatments. β-Ga₂O₃ samples with various morphologies were obtained by using different kinds of solvent, including water, isopropanol and ethylene glycol. One-dimensional β-Ga₂O₃ nanorods were obtained in water medium, while β-Ga₂O₃ spheres were prepared in alcohol. The possible mechanism related to the phase formation and morphology of the as-prepared materials was discussed. Photocatalytic performance of the synthesized β-Ga₂O₃ samples was also examined. Results revealed that β-Ga₂O₃ sample prepared with ethylene glycol showed the highest photocatalytic activity for the degradation of salicylic acid. This could be ascribed to the high surface area, abundant hydroxyl groups, and wide band gap of β-Ga₂O₃ sample synthesized in ethylene glycol.     

ZnO – Yb2O3 composite optical ceramics: Synthesis,structure and spectral-luminescent properties

Zinc oxide optical ceramics containing 0–2 wt% ytterbium are prepared by uniaxial hot pressing of commercial oxides at 1150 and 1180 °C. The ceramics have the main crystalline phase of hexagonal wurtzite-type ZnO. Ytterbium ions do not enter the ZnO crystals but form a cubic sesquioxide phase of Yb₂O₃ located at the ZnO grain boundaries. Yb acts as an inhibitor for the ZnO grain growth. The ceramics exhibit transmittance up to 60 % in the visible. Their transmission in the infrared is determined by the free charge carrier absorption. The Yb³⁺ ions are found in C₂ and C_3i sites in Yb₂O₃ crystals. Under X-ray excitation, the ceramics exhibit intense luminescence bands in the blue (near-band-edge emission) and green (defect emission) whose positions, intensities and decay times depend on the Yb content. Yb₂O₃ causes a redistribution of luminescence intensity in favor of the near-band-edge emission and fastens the emission decay.     

Novel supramolecular system of amphiphilic hyperbranched polymer with β-cyclodextrin and hyperbranched topography cavities: Synthesis and selective encapsulation

Novel supramolecular system of amphiphilic hyperbranched polymer with hyperbranched poly(β-cyclodextrin) core was designed and synthesized to accomplish a so-called selective encapsulation, where two types of guest molecules can be encapsulated into two types of molecular cavities from β-cyclodextrin (β-CD) and topography structure of hyperbranched polymer, respectively. The double molecular recognition behaviors from β-CD and hyperbranched cavities drive one guest to go into the former, the other guest to the latter. This selective encapsulation was further confirmed via the release profiles and sequences of Levofloxacin lactate (LL) and Phenolphthalein (PP). LL presents a sustained release period followed by an almost non-release stage, while PP releases on a quite slow rate at first, subsequently on the linearly increasing rate. At the early stage, the release of LL dominates in comparison with PP, and then the release rate of PP increases to play a determinate role in the release system. It can be attributed to the existence of two guests in the different molecular cavities with the different microenvironments. The observed selective encapsulation of supramolecular system is a new phenomenon, which is helpful to extend the application of CD-based hyperbranched polymers in supramolecular science and complex drug delivery system.     

Synthesis and electrochemical properties of α-LiVOPO4 as cathode material for lithium-ion batteries

Triclinic α-LiVOPO₄ with excellent electrochemical properties is prepared, using δ-VOPO₄, LiNO_3, and a highly conductive carbon material (acetylene black) as raw materials, by a two-step method, for the first time. Transmission electron microscopy reveals that the synthesized nanoscale α-LiVOPO₄ is approximately 50–100?nm in size, and its surface is covered by 1.68?nm thick acetylene black, which not only improves the ionic conductivity of the material, but prevents material-size growth at high temperature, and particle agglomeration. In addition, the initial discharge capacity of α-LiVOPO₄ sintered at 600?°C over 10?h is the highest, reaching 111.7?mAh?g^?1 at 0.05?°C. The capacity retention rate is 95.1%, which is 106.3?mAh?g^?1 after 50 cycles.     

High dielectric and microwave absorption properties of ultra-thin 1-xSrTiO3-δ − xSrAl12O19 films

To reduce the thickness of the microwave absorbing materials, we have prepared 1-xSrTiO_3-δ?xSrAl₁₂O₁₉ ceramics by hot?pressing sintering in the vacuum. The microstructure, dielectric, thermogravimetric analysis and microwave absorbing properties of 1-xSrTiO_3-δ?xSrAl₁₂O₁₉ were systematically investigated and discussed. The 0.95SrTiO_3-δ??0.05SrAl₁₂O₁₉ has high permittivity, the real part is from 1662.2 to 704.9 and the imaginary part is from 208.6 to 12. The absorption bandwidth (reflection loss ≤?5?dB) of 0.95SrTiO_3-δ??0.05SrAl₁₂O₁₉ can cover 8.6???12.4?GHz and its thickness is only 0.232?mm which is much thinner than these recently reported by other researchers. For 0.942SrTiO_3-δ??0.058SrAl₁₂O₁₉, the peak value of reflection loss is up to ??58.5?dB with a thickness of 0.75?mm. The 1-xSrTiO_3-δ?xSrAl₁₂O₁₉ films could be excellent candidates for highly efficient and ultra?thin microwave absorbing materials.     

Ionic transport properties and their variations with grain size in nanostructured double doped cerias such as Ce0.8Gd0.1Pr0.1O2−δ and Ce0.8Gd0.15Pr0.05O2−δ

This work presents the ionic transport properties in some nanocrystalline double doped cerias, i.e., Ce_0.8Gd_0.1Pr_0.1O_2−δ and Ce_0.8Gd_0.15Pr_0.05O_2−δ with various average grain sizes, in the intermediate temperature region. The correlations between electrical and dielectric properties of these materials have been established and variation of conductivity with respect to temperature has been thoroughly discussed. All the materials are found to be ionic in nature and show high value of ionic conductivity at intermediate temperatures. The nanocrystalline Ce_0.8Gd_0.1Pr_0.1O_2−δ material (irrespective of grain size), shows lowest association energy, i.e., 0.03 eV, which is close to the theoretically predicted lowest value (0.02 eV) in double doped ceria. A repulsive force is expected between the free oxygen vacancies at the grain boundary regions at higher temperatures, which restricts the rise in grain boundary conductivity and results in decrease in total conductivity.     

Synthesis and luminescence properties of Y2O2S:Dy,Mg, Tiphosphors prepared by sol–gel process

Y₂O₂S:Dy³⁺, Mg²⁺, Ti⁴⁺ white-light long-lasting phosphors were synthesized by sol–gel method. Y₂O₂S:Dy³⁺, Mg²⁺, Ti⁴⁺ phosphors were characterized by X-ray diffraction, photoluminescence spectroscopy and thermally stimulated spectrometry. The results showed that the samples calcined at different temperatures from 900 °C to 1200 °C were composed of the pure Y₂O₂S phase. Under 359 nm UV excitation, the phosphor presented white luminescence due to mixing of the dominating emissions centered at 488 nm (blue) and 579 nm (yellow), corresponding to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions of Dy³⁺, respectively. Both the fluorescence intensity and afterglow time reached the largest values in the phosphor calcined at 1200 °C and the afterglow time could last for over 65 min (≥1 mcd/m²) when the excited source was cut off.