Synthesis of terpyridine-functionalized poly(phenylenevinylene)s: The role of meta-phenylene linkage on the Cu and Zn chemosensors

A meta-phenylene-containing poly(phenylenevinylene) (PPV) with pendant terdentate terpyridine ligand 2b was synthesized and its fluorescence properties were compared with its isomeric PPV. The meta-phenylene bridge interrupts the resonance connection between the PPV backbone and the metal-chelation sites, while jointing the structurally defined chromophores together. The fluorescence of the polymer, with emission λ_em = 460 nm and ?_fl ≈ 0.45, is found to be selectively quenched by Cu²⁺ ion with interference from Co²⁺ and Ni²⁺ ions. The nature of the quenching process in 2b is probed by using Stern-Volmer analysis, revealing that the quenching results from both dynamic collision and metal chelation. Addition of Zn²⁺ and Cd²⁺ ions only induces partial fluorescence quenching, accompanied with a broad new emission band occurring at ∼560 nm. With the aid of a model compound study, the new emission band at 560 nm is attributed to the complex formation with terpyridine to Zn ratio of 1:1. The study finds that the polymer has the potential for Cu²⁺ and Zn²⁺ sensors.     

Synthesis,photo‐, and electroluminescent properties of the soluble poly[(2,5‐diphenylene‐1,3,4‐oxadiazole)‐ 4,4′‐vinylene]

A novel soluble conjugated polymer, poly[(2,5‐diphenylene‐1,3,4‐oxadiazole)‐4,4′‐vinylene] (O‐PPV), containing an electron‐transporting group on the main chain of PPV, was synthesized according to HORNER mechanism. The oligo‐polymer with M_w = 1000 and T_d = 270°C is soluble in chloroform and tetrahydrofuran. The photoluminescent (PL) properties were investigated using different concentrations of solid‐state O‐PPV/PEO blends absorption and selective excitation measurements. The results show that PL arises from interchain charge‐transfer states in solid‐state O‐PPV. Compared with the analogous single‐layer device constructed with PPV (ITO/PPV/Al), which emits two peaks at λ = 520 nm and 550 nm (shoulder), the electroluminescence (EL) spectrum of the device [ITO/O‐PPV (80 nm)/Al] is a broad peak at λ_max = 509 nm. The quantum efficiency (0.13%) of the device ITO/O‐PPV/Al is much higher than that of the device ITO/PPV/Al, due to the introduction of the electron‐transporting group–oxadiazole units in the main chain of PPV. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3535–3540, 1999     

Raman study of the temperature-induced decomposition of the two-dimensional rhombohedral polymer of C60 and the intermediate states formed

Raman spectra of single crystalline two-dimensional rhombohedral (2D-R) polymer of C₆₀ were measured at ambient conditions after its high temperature treatment (HTT) in order to study the polymer decomposition process. The data obtained indicate that the 2D-R polymer remains stable after 0.5 h treatment up to ∼503 K, while at higher temperatures a material transformation takes place. New Raman lines appear in the Raman spectrum after HTT in the range of 513-553 K, related to the A_g(2) pentagon pinch (PP) mode of 2D tetragonal-like (2D-T-like) and 1D orthorhombic-like (1D-O-like) oligomers as well as to C₆₀ dimers and monomers, typical for an intermediate state of partially decomposed 2D-R polymer. Above 553 K, the material changes completely and its new composition is dominated by C₆₀ monomers with some possible inclusion of C₆₀ dimers. The activation energy of the 2D-R polymer decomposition, obtained from the dependence of the decomposition time on the treatment temperature, is E_A = 1.76 ± 0.07 eV/molecule.     

Efficiency of C60 incorporation in and release from single-wall carbon nanotubes depending on their diameters

We show that the efficiency of incorporating C₆₀ in single-wall carbon nanotubes (SWCNTs) and that of the incorporated C₆₀’s release from the SWCNTs depend on the SWCNT diameter. Through transmission electron microscopy, we found that the C₆₀ incorporation efficiency reached its maximum at diameters of 1-2 nm, while the efficiency of C₆₀ release from SWCNTs in toluene was maximized at 3-5 nm. The difficulty of C₆₀ release from SWCNTs with diameters of 5-6 nm might reflect either the effective packing of C₆₀ inside SWCNTs or a flattened SWCNT structure. We occasionally observed C₆₀ molecules arranged in a line along the sidewall inside SWCNTs with large diameters/width (>7 nm), indicating that large diameter SWCNTs were sometimes flattened.     

Solvated structure of C60 nanowhiskers

This work characterizes the structure of C₆₀ nanowhiskers prepared by the liquid-liquid interfacial precipitation method in the C₆₀-saturated m-xylene and isopropyl alcohol system. Transmission electron microscopy and X-ray diffraction measurement show that the C₆₀ nanowhiskers had a hexagonal structure with cell dimensions a = 2.407 nm and c = 1.018 nm which is different from pristine C₆₀. The structure of the C₆₀ nanowhiskers in solution is different from that of the solvated structure reported for the C₆₀ nanotubes but similar to that reported for the C₆₀ bulk crystal solvated with m-xylene. X-ray diffraction analysis also showed a shift to fcc structure after solvent evaporation. The C₆₀ nanowhiskers prepared using toluene as solvent also showed a similar solvated structure, and a more rapid structural change into fcc upon drying was again observed.     

Fluorescence spectra of poly(di-n-hexylsilane)/TiO2 nanoparticle hybrid film

The interaction between poly(di-n-hexylsilane) (PDHS) and TiO₂ nanoparticle was studied based on the temperature dependence of the fluorescence of a PDHS/TiO₂ nanoparticle hybrid film. The polysilane is a suitable probe to investigate a guest polymer-host matrix interaction because the photophysical properties of polysilanes remarkably depend on the conformation of the σ-conjugated Si-Si chain. The PDHS/TiO₂ nanoparticle hybrid film showed a fluorescence band assigned to a disordered structure even at 80 K whereas only the fluorescence band of an ordered structure was observed for the PDHS film at 80 K. The disordering of the Si-Si main chain was explained by the perturbation of the n-hexyl side chain in the neighborhood of the TiO₂ nanosurface. The non-radiative deactivation of the excited state via the disorder-induced local potential minima was suggested by the temperature dependence of the fluorescence intensities of the disordered and ordered structures in the temperature region from 80 to 160 K.     

High rate performance of highly dispersed C60 on activated carbon capacitor

Fullerene-activated carbon composite electrodes were prepared and their charge/discharge characteristics were studied for use in a high power electric double-layer capacitor. The capacitance of the C₆₀-loaded activated carbon fiber (ACF) electrodes became greater than that of the unloaded ACF at charge/discharge current densities above 50 mA/cm². In order to obtain a highly dispersed C₆₀-loaded electrode, an ultrasonic treatment was performed. The size of the C₆₀ agglomerate decreased from 1-2 to 0.1 μm or less, and the capacitance of the C₆₀-loaded ACF electrodes increased with an increase in the ultrasonic treatment time. A higher capacitance of 172 F/g was obtained at 50 mA/cm² on a 1 wt% C₆₀-loaded electrode with ultrasonic treatment, and the C₆₀-loaded ACF electrode also showed a higher cycle performance.     

Synthesis and properties of various PPV derivatives with phenyl substituents

New electroluminescent polymers with various phenyl groups, poly[2-dimethyl(octyl)silyl-5-(4-(dimethyl(octyl)silyl)phenyl)-1,4-phenylenevinylene] (P1), poly[2,5-bis(4-(dimethyl(octyl)silyl)phenyl)-1,4-phenylenevinylene] (P2), poly[2,5-bis(9,9-dihexylfluorenyl)-1,4-phenylenevinylene] (P3), and poly[2,5-bis(4-(4-(2-etylhexyloxy)phenyl)phenyl)-1,4-phenylenevinylene] (P4), have been synthesized by the Gilch polymerization. The maximum absorption peaks of P1-P4 appeared at 388-423 nm in THF solution, and are red-shifted to 404-425 nm in solid thin film. The photoluminescence (PL) emission spectra of P1-P4 show a maximum peak at 482-503 nm in THF solution and at 521-549 nm as the solid film state. The emission spectra in the solid film state are more red-shifted over 40 nm, and the full width at half maximum (fwhm) was 30 nm greater than the solution conditions. The polymer light-emitting diodes (PLEDs) with the configuration of ITO/PEDOT/polymer/Al emitted light with maximum peaks at around 517-546 nm. The various phenyl substituents, with intermolecular interactions in the solid film state, can introduce the color tuning and device performance enhancement of the conjugated polymer as an emissive layer in PLED.     

Synthesis of nanocrystalline ytterbium-doped yttria by citrate-gel combustion method and fabrication of ceramic materials

Nanosized ytterbium doped yttria powders were prepared by citrate-gel combustion techniques. As-synthesized precursor and calcined powders were characterized for their crystalline structure, particle size and morphologies. Nanocrystalline Yb³⁺:Y₂O₃ powders with pure cubic yttria crystal structure were obtained by calcination of as-prepared precursors at 1100 °C for 3 h. Powders obtained were well dispersed with an average particle size of 60 nm. By using the obtained powders, nearly full dense Yb³⁺:Y₂O₃ ceramics were produced by vacuum sintering at 1800 °C for 12 h. The emission spectrum of the sintered ceramics under the excitation wavelength of 905 nm illustrates that there are three fluorescence peaks locating at 976 nm, 1030 nm and 1075 nm respectively, all corresponding to the ²F_5/2 → ²F_7/2 transitions of ytterbium ion.     

Synthesis and luminescence properties of nitrided lanthanum magnesium hexaluminate LaMgAl11O19 phosphors

Nitrided LaMgAl₁₁O₁₉ phosphors were prepared by a two-step method involving synthesis at 1550 °C for 4 h, trituration, and firing at 1650 °C for 5 h under a nitrogen atmosphere. Nitrogen was doped into LaMgAl₁₁O₁₉ and bonded with aluminium atoms. The nitrided LaMgAl₁₁O₁₉ phosphors showed plate-like morphology with a rough surface and exhibited strong blue emission at 442 nm and 450 nm, which may be attributed to the energy transition between defect levels. A weak emission band at 590 nm was ascribed to the transition between the V_Al acceptor and the valence band, which was excited at 254 nm.     

Characteristics of solubilization and encapsulation of fullerene C60 in non-ionic Triton X-100 micelles

The solubilization and encapsulation of monomeric C₆₀ in Triton X-100 micelles were investigated. Characteristic hydrophobic interactions of the type π-π and CH-π between the Triton X-100 micelle and C₆₀ resulted in stable aqueous dispersions of C₆₀ in the micellar medium, as evidenced from UV-vis, fluorescence emission and micro-Raman spectroscopy. Cyclic voltammetry of C₆₀ encapsulated Triton X-100 in aqueous 5 mM LiClO₄ solution revealed a quasi-reversible one-electron reduction peak with E_1/2 = −0.61 V and a reversible reduction peak at E_1/2 = −1.11 V vs. Ag/AgCl reference electrode at a scan rate of 10 mV s⁻¹, a redox behaviour drifting substantially from that of pure C₆₀. An onset concentration of ∼0.025 mM for C₆₀ aggregation in the micellar core was substantiated from the characteristic absorption spectral broadening and quenching of pyrene fluorescence. The molar solubilization capacity of C₆₀ in aqueous Triton X-100 micellar solution was estimated spectrophotometrically to be 0.22.     

Deposition of amorphous carbon films from C60 fullerene sublimated in electron beam excited plasma

C₆₀ fullerene clusters are used as a carbon source for amorphous carbon films deposition in an electron beam excited plasma. C₆₀ clusters are sublimated by heating a ceramic crucible containing the C₆₀ powders up to 850 °C, which is located in a highly vacuumed process chamber. The sublimated fullerene powders are injected to the electron beam excited argon plasma and dissociated to be active species that are propelled toward the substrates. Consequently, the carbon species condense as a thin film onto the negatively biased substrates that are immersed in the plasma. Deposition rates of approximately 1.0 μm/h and the average surface roughness of 0.2 nm over an area of 400 μm² are achieved. Decomposition of the C₆₀ fullerene after injecting into the plasma is confirmed by optical emission spectroscopy that shows existence of small carbon species such as C₂ in the plasma. X-ray diffraction pattern reveals that the microstructure of the film is amorphous, while fullerene films deposited without the plasma show crystalline structure. Raman spectroscopic analysis shows that the films deposited in the plasma are one of the types of diamond-like carbon films. Different negative bias voltages have been applied to the substrate holder to examine the effect of the bias voltage to the properties of the films. The nano-indentation technique is used for hardness measurement of the films and results in hardness up to about 28 GPa. In addition, the films are droplet-free and show superior lubricity.     

Self-assembly of C60 containing poly(methyl methacrylate) in ethyl acetate/decalin mixtures solvent

[60]Fullerene (C₆₀) was mono-substituted with well-defined poly(methyl methacrylate) (PMMA-b-C₆₀) using the atom transfer radical polymerization (ATRP) technique. The self-assembly behaviors of PMMA-b-C₆₀ in ethyl acetate (EA) and decalin mixtures were studied using laser light scattering (LLS) and transmission electron microscopy (TEM). Homogeneous solutions of PMMA-b-C₆₀ can be obtained in the solvent mixtures containing more than 40 wt% EA, where the molar ratio of decalin to EA is close to 1. For each solvent mixture, unimers coexist with micelles and large aggregates. The sizes of PMMA-b-C₆₀ micelles and aggregates are independent of polymer concentration, confirming that they are produced via the closed association mechanism. For the various solvent mixtures, the weight-averaged molecular weights, M_w of the PMMA-b-C₆₀ aggregates range from 4.1×10⁷ to 12.5×10⁷ g/mol. The hydrodynamic radii of the large aggregate, R_h, vary from 90 to 136 nm, while the z-averaged radii of gyration, R_g, range from 210 to 311 nm. The R_g/R_h value for each solvent mixture is ∼2.3, which is independent of decalin contents in the mixed solvents. The morphological study using the transmission electron microscope suggests that the large aggregates are composed of porous large compound micelles (LCM) in solution.     

C60 fullerene inclusions in low-molecular-weight polystyrene-poly(dimethylsiloxane) diblock copolymers

We have synthesized low-molecular-weight diblock copolymers of polystyrene-block-poly(dimethylsiloxane) with total molecular weights <12 kg/mol and PS volume fractions of ∼0.2. We have investigated the phase behavior of the PS-PDMS in its pure state and with up to 10 wt% of C₆₀ added. The C₆₀ was shown to selectively segregate into the PS phase only although its solubility limit is ∼1 wt%. Although the C₆₀ aggregates above 1 wt%, the cylindrical morphology observed in the pure copolymer bulk samples persists in the C₆₀-copolymer composites even up to 10 wt% C₆₀ loading. In thin films, the pure copolymer possesses a highly ordered morphology with grains hundreds of microns across. When C₆₀ is blended with the copolymer the high degree of order rapidly decreases due to increasing numbers of defects observed.     

The intercalation of C60-containing PEO into layered MnPS3

This paper reports the synthesis and magnetism of a new polymer-inorganic intercalation nanocomposite based on a C₆₀-containing poly(ethylene oxide) (C₆₀-PEO) into layered MnPS₃, which is characterized by XRD, IR and thermal analyses. The lattice expansion (Δd) of the intercalation nanocomposite is about 9.3 Å indicating the successful intercalation. And the charge balance is maintained by K⁺ ions coordinating with PEO chain of C₆₀-PEO polymer, which come from the pre-intercalation compound Mn_1−xPS₃[K_2x(H₂O)_y]. Magnetic measurements indicate that the intercalation nanocomposite (C₆₀-PEO/MnPS₃) exhibits a magnetic phase transition from paramagnetism to ferrimagnetism at about 40 K. And the distinctive hysteresis of M-H relationship further confirms that it is a low temperature ferrimagnetic nanocomposite.     

Cross-sectional structural analysis of C60 nanowhiskers by transmission electron microscopy

Cross-sectional observations of C₆₀ nanowhiskers (C₆₀NWs) were successfully conducted using the focused ion beam (FIB) method. The C₆₀NWs were observed to possess the core-shell structures with porous cores and dense surface thin layers. The size and number of pores decreased from the center to the surface, showing that the densification of C₆₀NWs proceeds from the surface to the center upon drying. A cross-sectional high-resolution transmission electron microscopy (HRTEM) image of a C₆₀NW showed a disordered structure comprising the domains with sizes on the order of 10 nm. The most frequently observed cross-sections were hexagons, reflecting the solvated hexagonal crystal structures of as-grown C₆₀NWs. From the observation of various cross-sectional shapes of C₆₀NWs with different diameters and crystallographic surface analysis, it is suggested that C₆₀NWs grow longer above a critical diameter D_c with the development of low-energy crystal surfaces.     

Fluorescent coumarin derivatives with large stokes shift, dual emission and solid state luminescent properties: An experimental and theoretical study

Coumarin derivatives containing 8-benzothiazole (C-2) and its difluoroboron bound derivative (C-3) were prepared. Both derivatives show dual emission at 322 nm and 513 nm and large Stokes shift (188 nm), compared to the unsubstituted coumarin (C-1), which shows emission at 356 nm with small Stokes shift of 46 nm. C-2 and C-3 show fluorescence in solid state, in contrast the C-1 is non-fluorescent in the solid state. The excited state intramolecular proton transfer (ESIPT) process of C-2 was fully rationalized by DFT/TDDFT calculations with optimization of the ground state (S₀) and excited state (S₁) geometries. TDDFT calculations propose that the large Stokes shift of C-2 and C-3 are due to the re-distribution of the frontier molecular orbitals at excited states. Study of the potential energy curve of C-2 indicated that the dual emission of the C-2 is due to the simultaneous S₁ and S₃ emission, not the rotamer of the enol form.     

Hexadecyl-functionalized lamellar mesostructured silicates and aluminosilicates designed for polymer-clay nanocomposites. Part I. Clay synthesis and structure

Motivated by a need for synthetic clays that can be dispersed and exfoliated in polymer melts without added compatibilizers, lamellar mesostructured silicates and aluminosilicates with covalently attached hexadecyl functional groups (C₁₆-LMS and C₁₆-LMAS, respectively) were prepared by sol-gel syntheses and their structures were characterized. Based on XRD and TEM data, lamellar products with layer spacings of 4.8-4.9 nm were obtained between room temperature and 60 °C (C₁₆-LMS) or 70 °C (C₁₆-LMAS). The degree of condensation of the aluminosilicate layers increased at the higher synthesis temperatures. Attachment of organic groups to the inorganic sheets was confirmed by ²⁹Si solid state MAS NMR and IR spectroscopy. The sheets of C₁₆-LMS consisted of single or double layers of tetrahedral silicate groups, each attached to a hexadecyl chain. C₁₆-LMAS was composed of pyrophyllite-like layers (Si:Al=2) with an octahedral aluminum layer sandwiched between two tetrahedral silicate layers and hexadecyl surface groups. Tetrahedral aluminum sites were also present. The clay layer spacing could be increased to 5.2 nm by addition of tetraethoxysilanes during the synthesis (C₁₆-SiO₂-LMAS). C₁₆-SiO₂-LMAS was structurally similar to C₁₆-LMAS; however, the presence of additional silicate groups in this structure increased the inorganic layer thickness and introduced further structural disorder.     

Scandium ion doped yttrium oxide transparent ceramic from nitrate alanine microwave combustion synthesized nanopowders

One atomic percent Neodymium ion doped Yttrium oxide, with 25 at% scandium ion (Nd_0.02Sc_0.5Y_1.48O₃), was synthesized by nitrate alanine microwave gel combustion followed by calcinations at 1000 °C for 2 h. Phase purity of nanopowder was characterized by X-Ray Diffraction (XRD). Neodymium and scandium ion doping was confirmed by cell parameter calculation and Scanning Electron Microscope-Electron Dispersive X-ray (SEM-EDX) analysis. Particles with size range 25–35 nm with close to spherical shape were obtained as observed by Transmission Electron Microscopy (TEM). Powder on compaction followed by vacuum sintering at 1765 °C for 40 min led to the formation of ceramic with 76% transmission at 2500 nm compared to translucent ceramic obtained without scandium ion doping. This indicates formation of highly sinterable neodymium doped yttrium oxide nanopowders by nitrate alanine microwave gel combustion route with scandium ion additive. Further the absorption and emission bands of Nd_0.02Sc_0.5Y_1.48O₃ are inhomogeneously broadened and fluorescence lifetime is longer than Nd_0.02Y_1.98O₃.     

The influence of tetrakis-ethylhexyloxy groups substituted in PPV derivative for PLEDs

New electroluminescent polymer with tetrakis-alkoxy group, poly[2,3,5,6-tetrakis(2-ethylhexyloxy)-1,4-phenylenevinylene] (TEH-PPV), has been synthesized by the Gilch polymerization. In solid film state, the TEH-PPV exhibits absorption spectra with maximum peaks at 451 nm, and PL spectrum at 505-545 nm. As compared to MEH-PPV, TEH-PPV with tetrakis-ethylhexyloxy groups in phenylene unit can get shorter conjugation length, and had more blue shifted absorption and emission peaks due to steric hindrance, in spite of increasing the number of alkoxy substituents which may increase the effective conjugation length caused by the electron-donating effect. The polymer LEDs (ITO/PEDOT/polymer/Al) of TEH-PPV showed emission with maximum peaks at around 505-590 nm. Tetrakis-ethylhexyloxy groups induced very typical vibronically structured band in solid film state, since the conjugated backbone is twisted by steric hindrance. And they can enhance the internal efficiency of the conjugated polymer as emissive layer in PLED because of the restraint of inter-chain interaction by the avoidance of close packing to give decent device performance.