A three-dimensional metal-organic framework based on a triazine derivative: syntheses, structure analysis, and sorption studies

A novel metal-organic framework [Cu-3(m-TATB)(2)Py(CH3OH)(2)] (1) constructed of a triazine-based trigonal-planar ligand, 3,3',3 ''-s-triazine-2,4,6- triyltribenzoate (m-H(3)TATB), has been synthesized and structurally characterized. Compound 1 features three-dimensional (3D) channels and cavities together, and exhibits high carbon dioxide sorption at normal pressure.

The first liquid crystalline phthalocyanine derivative capable of edge-on alignment for solution processed organic thin-film transistors

Tetraoctyl-substituted vanadyl phthalocyanine (OVPc4C8) as a new NIR-absorbing discotic liquid crystalline material can form highly ordered thin films with edge-on alignment of the molecules and molecular packing mode identical to that in the phase II of OVPc for solution processed OTFTs with mobility up to 0.017 cm(2) V-1 s(-1).

Synthesis and Characterization of Coil-Rod-Coil Triblock Copolymers Comprising Fluorene-Based Mesogenic Monodisperse Conjugated Rod and Poly(ethylene oxide) Coil

A series of coil-rod-coil triblock copolymers (i.e., F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125) with a mesogenic monodisperse conjugated oligomer comprising 3 fluorene, 8 thiophene, and 2 phenyl units as the rod and poly(ethylene oxide) (PEO) as the coil were synthesized. A reference compound, that is F3T8ME2, with the identical rod but without PEO was also prepared for comparison. The volume fraction of PEO (f(PEO)) was 0, 0.16, 0.28, 0.50, and 0.73 for F3T8ME2, F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125, respectively. It was found that the introduction of PEO into the triblock copolymers encouraged the formation of H-type aggregation and f(PEO)-dependent highly ordered mesophases while f(PEO) < 0.73. For F3T8ME2, only nematic mesophase was observed. In contrast, F3T8EO8 and F3T8EO17, with f(PEO) of 0.16 and 0.28, respectively, are smectic A (SA) mesomorphism.

Fluorene-Based Copolymers Containing Dinaphtho-s-indacene as New Building Blocks for High-Efficiency and Color-Stable Blue LEDs

By incorporating a new building block, 7,7,15,15-tetraoctyldinaphtho-s-indacene (NSI), into the backbone of poly(9,9-dioctylfluorene) (PFO), a novel series of blue light-emitting copolymers (PFO-NSI) have been developed. The insertion of the NSI unit into the PFO backbone leads to the increase of local effective conjugation length, to form low-energy fluorene-NSI-fluorene (FNF) segments that serve as exciton trapping sites, to which the energy transfers from the high-energy PFO segments. This causes these copolymers to show red-shifted emissions compared with PFO, with a high efficiency and good color stability and purity. The best device performance with a luminance efficiency of 3.43 cd . A(-1), a maximum brightness of 6 539 cd . m(-2) and CIE coordinates of (0.152, 0.164) was achieved.

Water-soluble phosphate-functionalized polyfluorene as fluorescence biosensors toward cytochrome c

An anionic water-soluble polyfluorene derivative, poly(9,9-bis(6'-phosphatehexyl)fluorene-alt-1,4-phenylene) sodium salt (PFHPNa), was synthesized by Suzuki coupling reaction in DMF/water. Polymer PFHPNa was well soluble in water with a strong blue fluorescence emission. Effect of the side chain length on fluorescence sensory properties was studied by comparing quenching efficiencies toward different quenchers of PFHPNa with a reported polymer poly(9,9-bis(3'-phosphatepropyl)fluorene-alt-1,4-phenylene) sodium salt (PFPPNa), which have different side chains in length. For small molecular quenchers (methylviologen, MV2+) and meso-5,10,15,20-tetrakis-(N-methyl-4-pyridyl)porphine (TMPyP4), polymer PFHPNa had lower sensitivity due to the much longer side chain length. The positively charged metalloprotein cytochrome c could quench fluorescence of conjugated polymers via energy transfer and electron transfer.

Efficient Electrophosphorescence from a Platinum Metallopolyyne Featuring a 2,7-Carbazole Chromophore

The synthesis, thermal and emission properties of an electrophosphorescent platinum(II) metallopolyyne polymer consisting of 9-butylcarbazole-2,7-diyl spacer P1 are described. The optical and electronic properties of P1 are compared to their molecular diplatinum(II) and digold(I) model complexes. The photophysical properties of P1 are somehow analogous to its 2,7-fluorene-linked congener but differs significantly from that for the 3,6-carbazole derivative. Its optical band gap is notably reduced as compared to that for the 3,6-carbazole analog. Multi-layer polymer light-emitting diodes (PLEDs) were fabricated with P1 as the emitting layer which gave a strong green-yellow electrophosphorescence. The best PLED can reach the maximum current efficiency of 4.7 cd . A(-1) at 5 wt.-% doping level, corresponding to an external quantum efficiency of 1.5%. This represents the first literature example of efficient PLEDs exhibiting pure triplet emission under electrical excitation for metallopolyynes without the concomitant singlet emission.

A Fully Diarylmethylene-Bridged Triphenylamine Derivative as Novel Host for Highly Efficient Green Phosphorescent OLEDs

A fully diarylmethylene-bridged triphenylamine derivative is efficiently synthesized. It has an almost planar triphenylamine (TPA) skeleton and exhibits excellent thermal and morphological stability. Devices with the novel TPA derivative as host material and Ir(ppy)(3) as triplet emitter show a maximum current efficiency of 83.5 cd/A and a maximum power efficiency of 71.4 Im/W for green electrophosphorescence.

Synthesis and characterization of monodisperse oligo(fluorene-co-bithiophene)s

A series of monodisperse oligo(9,9-di-n-octylfluorene-co-bithiophene)s (OFbTs) with molecular lengths of up to 19.5 nm and molecular weights up to 7025 g mol(-1) has been synthesized by a divergent/convergent approach involving Stille coupling reactions. Stille coupling is quite efficient in preparing this class of oligomers, and even the molecule with nine fluorene units and eight bithiophene units (F9Th16) can be synthesized in a yield as high as 70%. Because of easy functionalization of the thiophene ring at its alpha position, no additional protecting group allowing activation for further reaction is necessary. However, the synthetic routes must be optimized to eliminate contamination of the targeting compounds with the homocoupling product of the organotin reagents. Synthesis of the longest oligomer F13Th24 in a relative large quantity is limited by its low yield due to the pronounced ligand-exchange side reactions of the starting materials and reaction intermediates. All oligomers longer than F4Th6 are nematic mesomorphs and exhibit enhanced glass transition temperature and clearing point with increasing molecular length, as revealed by differential scanning calorimetry and polarizing optical microscopy.

Stimulated emission from distyrylbenzene derivative crystals grown by vapor

Narrowed spectra at 452 nm from a thin platelike crystal of distyrylbenzene derivative, 2,5-diphenyl-1,4-distyrylbenzene with two trans double bonds (trans-DPDSB) grown by vapor deposition, are observed. The trans-DPDSB crystal is irradiated by the third harmonic (355 nm) of a Nd:YAG laser. The FWHM of the narrowed spectra can reach 6 nm for the crystal when the pumping energy is 400 mu J/pulse. The threshold value for an optically pumped laser is approximately 350 mu J/pulse.

Synthesis of PAMAM dendrimers bearing BINOL derivative

New functional dendrimers bearing 4, 8 and 16 axial chiral units on their surface were synthesized from achiral PAMAM dendrimers and axial chiral (R)-BINOL derivative.

Crosslinkable poly (p-phenylenevinylene) derivative

To simplify the fabrication of multilayer light-emitting diodes, we prepared a p-phenylenevinylene-based polymer capped with crosslinkable styrene through a Wittig reaction. Insoluble poly(p-phenylenevinylene) derivative (PPVD) films were prepared by a thermal treatment. The photoluminescence and ultraviolet-visible (UV-vis) absorbance of crosslinked films and noncrosslinked films were studied. We also studied the solvent resistance of crosslinked PPV films with UV-vis absorption spectra and atomic force microscopy. Double-layer devices using crosslinked PPVD as an emitting layer, 2-(4-tert-butylphenyl)-5-phenyl-1,3,4-oxadiazole (PBD) in poly(methyl methacrylate) as an electron-transporting layer, and calcium as a cathode were fabricated. A maximum luminance efficiency of 0.70 cd/A and a maximum brightness of 740 cd/m(2) at 16 V were demonstrated. A 12-fold improvement in the luminance efficiency with respect to that of single-layer devices was realized.

Blue light-emitting poly(fluorene-co-benzene) containing an oxadiazole moiety

A new kind of polyfluorene containing oxadiazole as the side chain was synthesized. The introduction of oxadiazole moiety as more bulky group prevents the aggregation and reduces the crystallinity of the polymers. Efficient intramolecular energy transfer from oxadiazole moiety to the conjugated backbone has been realized, leading to 70% improvement of photoluminescence quantum efficiency of the designed polymers. Compared with PAF, the PFOXD exhibits significant improvement in electroluminescence properties, with luminous efficiency of 0.8 cd/A and maximum luminance of 1800 cd/m(2).

White electrolumineseence from a single-polymer system with simultaneous two-color emission: Polyfluorene as the blue host and a 2,1,3-benzothiadiazole derivative as the orange dopant on the main chain

New single-polymer electroluminescent systems containing two individual emission species - polyfluorenes as a blue host and 2,1,3-benzothiadiazole derivative units as an orange dopant on the main chain - have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue(lambda(max) = 421 nm/445 nm) and orange emission (lambda(max) = 564 nm)from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light-emitting diodes (PLEDs) based on the single-polymer systems has been investigated. The introduction of the highly efficient 4,7-bis(4-(N-phenyl-N-(4-methylphenyl)amino)phenyl)-2,1,3-benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single-layer device fabricated in air (indium tin oxide/poly(3,4-ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure-white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m(-2), luminance efficiency of 7.30 cd A(-1), and power efficiency of 3.34 lm W-1 can be obtained.

Negative differential resistance effect in organic devices based on an anthracene derivative

The authors observed a negative differential resistance (NDR) in organic devices consisting of 9,10-bis-(9,9-diphenyl-9H-fluoren-2-yl)-anthracene (DPFA) sandwiched between Ag and indium tin oxide electrodes. The large NDR shown in current-voltage characteristics is reproducible, resulting in that the organic devices can be electrically switched between a high conductance state (on state) and a low conductance state (off state). It can be found that the currents at both on to off states are space-charge limited and attributed to the electron traps at the Ag/DPFA interface. The large and reproducible NDR makes the devices of tremendous potential in low power memory and logic circuits.

Synthesis of fluorene-based oligomeric organoboron reagents via Kumada, Heck, and stille cross-coupling reactions

Boronic pinacol ester group is not reactive in Kumada, Heck and Stille coupling reaction conditions. Fluorene-based sophisticated organoboron compounds were synthesized by means of Palladium catalyzed Kumada, Heck and Stille cross-coupling reactions from halofluorenyl boronic esters.