Synthesis of redox-active, intramolecular charge-transfer chromophores by the [2+2] cycloaddition of ethynylated 2H-cyclohepta[b]furan-2-ones with tetracyanoethylene

Ethynylated 2H-cyclohepta[b]furan-2-ones 5-15 have been prepared by Pd-catalyzed alkynylation of 3-iodo-5-isopropyl-2H-cyclohepta[b]furan-2-one (2) with the corresponding ethynylarenes or the reaction of 2-iodothiophene with 3-ethynyl-5-isopropyl-2H-cyclohepta[b]furan-2-one (4) under Sonogashira-Hagihara conditions. Compounds 5-15 reacted with tetracyanoethylene in a formal [2+2] cycloaddition reaction, followed by ring opening of the initially formed [2+2] cycloadducts, cyclobutenes, to afford the corresponding 1,1,4,4-tetracyanobutadienyl (TCBD) chromophores 16-26 in excellent yields. The intramolecular charge-transfer interactions between the 2H-cyclohepta[b]furan-2-one ring and TCBD acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel TCBD derivatives 16-26 was examined by cyclic voltammetry and differential pulse voltammetry, which revealed multistep electrochemical reduction properties, depending on the number of TCBD units in the molecule. Moreover, a significant color change was observed by UV/Vis spectroscopy under electrochemical reduction conditions.     

Excitation energy migration in oligo(p-phenylenevinylene) based organogels: structure-property relationship and FRET efficiency

Excitation energy migration (EM) and assisted energy transfer (ET) properties of a few oligo(p-phenylenevinylene) (OPV) based organogelators with different end functional groups have been studied using picosecond time-resolved emission spectroscopy (TRES). EM was found to be more efficient in OPV gelators with small end functional groups (OPV3-4) when compared to that of the gelators with bulky end groups (OPV1-2) in the gel state. TRES studies at elevated temperature and in chloroform solution highlight the role of the self-assembled scaffolds in assisting the EM and ET processes. Increase in temperature and solvent polarity leads to the aggregate breaking and hence adversely affects the EM and ET efficiencies. The effect of EM efficiency on the fluorescence resonance energy transfer (FRET) properties of the OPV gels was studied by using OPV1 and OPV3 as the donors and OPV5 as the acceptor. Better transfer of excitation energy was observed in the donor system (OPV3) having higher EM efficiency even at very low concentration (3.1 mol%) of the acceptor molecules, whereas ET efficiency was lower in the donor system (OPV1) with low EM efficiency.     

Excited-State Electron Transfer in 1,1,4,4-Tetracyanobuta-1,3-diene (TCBD)- and Cyclohexa-2,5-diene-1,4-diylidene-Expanded TCBD-Substituted BODIPY-Phenothiazine Donor–Acceptor Conjugates

A new set of donor–acceptor (D–A) conjugates capable of undergoing ultrafast electron transfer were synthesized using 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-substituted phenothiazine, SM1–SM3 , by a Pd-catalyzed Sonogashira cross-coupling reaction and a [2+2] cycloaddition–electrocyclic ring-opening reaction. The incorporation of 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (abbreviated as DCNQ=dicyanodiquinodimethane) in BODIPY-substituted phenothiazine resulted in significant perturbation of the optical and electronic properties. The absorption spectrum of both SM2 and SM3 showed red shifted absorption as compared to SM1 . Additionally, both SM2 and SM3 exhibited a distinct intramolecular charge-transfer (ICT) transition in the near-IR region more so for SM3 . The electrochemical study revealed multi-redox processes due to the presence of redox-active phenothiazine, BODIPY, TCBD or DCNQ entities. Using data from spectral, electrochemical and computational studies, an energy-level diagram was established to witness excited-state electron-transfer events. Finally, evidence of electron transfer and their kinetic information was secured from studies involving a femtosecond transient absorption technique. The time constants for excited-state electron-transfer events in the case of SM2 and SM3 were less than 5 ps revealing ultrafast processes.     

Ultrasonic approach for formation of erbium oxide nanoparticles with variable geometries

Ultrasound (20 kHz, 29 W·cm(-2)) is employed to form three types of erbium oxide nanoparticles in the presence of multiwalled carbon nanotubes as a template material in water. The nanoparticles are (i) erbium carboxioxide nanoparticles deposited on the external walls of multiwalled carbon nanotubes and Er(2)O(3) in the bulk with (ii) hexagonal and (iii) spherical geometries. Each type of ultrasonically formed nanoparticle reveals Er(3+) photoluminescence from crystal lattice. The main advantage of the erbium carboxioxide nanoparticles on the carbon nanotubes is the electromagnetic emission in the visible region, which is new and not examined up to the present date. On the other hand, the photoluminescence of hexagonal erbium oxide nanoparticles is long-lived (μs) and enables the higher energy transition ((4)S(3/2)-(4)I(15/2)), which is not observed for spherical nanoparticles. Our work is unique because it combines for the first time spectroscopy of Er(3+) electronic transitions in the host crystal lattices of nanoparticles with the geometry established by ultrasound in aqueous solution of carbon nanotubes employed as a template material. The work can be of great interest for "green" chemistry synthesis of photoluminescent nanoparticles in water.     

Fabrication of color-tunable luminescent silica nanotubes loaded with functional dyes using a sol-gel cocondensation method

Luminescent silica nanotubes SNT-2 (loaded with coumarion laser dye 2) and SNT-3 (loaded with anthracene laser dye 3) were prepared by sol-gel cocondensation of functional dyes and TEOS in a cholesterol-based organogel system. The emission colors of silica nanotubes were tuned by using different functional dyes. Interestingly, there is a great difference in PL spectrum of silica nanotubes loaded with functional dyes between ethanol and the solid state. In ethanol, a green light emission of SNT-2 and a bluish green light emission of SNT-3 were observed at 486 and 465 nm, respectively, because of the anchoring state between the dye and the tube, whereas in the solid state, strong blue light emissions of SNT-2 and SNT-3 were observed at 482 and 483 nm, respectively, because of the intense emission of the silica nanotube (SNT) itself rather than that of 2 and 3.     

Efficient Intramolecular Energy Transfer between Two Fluorophores in a Bis‐Branched [3]Rotaxane

A bis‐branched [3]rotaxane, with two [2]rotaxane arms separated by an oligo(para‐phenylenevinylene) (OPV) fluorophore, was designed and investigated. Each [2]rotaxane arm employed a difluoroboradiaza‐s‐indacene (BODIPY) dye‐functionalized dibenzo[24]crown‐8 macrocycle interlocked onto a dibenzylammonium in the rod part. The chemical structure of the [3]rotaxane was confirmed and characterized by ¹H and ¹³C NMR spectroscopy and high‐resolution ESI mass spectrometry. The photophysical properties of [3]rotaxane and its reference systems were investigated through UV/Vis absorption, fluorescence, and time‐resolved fluorescence spectroscopy. An efficient energy‐transfer process in [3]rotaxane occurred from the OPV donor to the BODIPY acceptor because of the large overlap between the absorption spectrum of the BODIPY moiety and the emission spectrum of the OPV fluorophore; this shows the important potential of this system for designing functional molecular systems.     

Effect of the Bulkiness of the End Functional Amide Groups on the Optical,Gelation, and Morphological Properties of Oligo(p‐phenylenevinylene) π‐Gelators

Herein, we describe the role of end functional groups in the self‐assembly of amide‐functionalized oligo(p‐phenylenevinylene) (OPV) gelators with different end‐groups. The interplay between hydrogen‐bonding and π‐stacking interactions was controlled by the bulkiness of the end functional groups, thereby resulting in aggregates of different types, which led to the gelation of a wide range of solvents. The variable‐temperature UV/Vis absorption and fluorescence spectroscopic features of gelators with small end‐groups revealed the formation of 1D H‐type aggregates in CHCl₃. However, under fast cooling in toluene, 1D H‐type aggregates were formed, whereas slow cooling resulted in 2D H‐type aggregates. OPV amide with bulky dendritic end‐group formed hydrogen‐bonded random aggregates in toluene and a morphology transition from vesicles into fibrous aggregates was observed in THF. Interestingly, the presence of bulky end‐group enhanced fluorescence in the xerogel state and aggregation in polar solvents. The difference between the aggregation properties of OPV amides with small and bulky end‐groups allowed the preparation of self‐assembled structures with distinct morphological and optical features.     

纳米CaCO3负载过渡金属CVD法制备多壁碳纳米管的研究

以纳米碳酸钙粉体为载体,用浸渍法制备了可用于化学气相沉积(CVD)法制备碳纳米管的高产率催化剂.应用FESEM,HRTEM,TEM,XRD和激光拉曼谱对产物进行了表征.结果表明,由于纳米碳酸钙具有较大的比表面积,可高密度地承载催化剂活性组分.在碳纳米管生长初期,处于缓慢分解状态的纳米碳酸钙才能有效地起到载体作用,且反应温度为700～750℃时,碳纳米管的产率较高.Fe-Co双金属催化剂在700℃,催化生长60min后,可增重10倍,而且产物中无定形碳含量极少.纳米碳酸钙载体易于提纯,用质量分数为30%的硝酸超声提纯粗产品1h,可使纯度提高到97%,且不破坏碳纳米管结构.     

The effect of annealing temperatures on surface properties,hydroxyapatite growth and cell behaviors of TiO2 nanotubes

Well‐ordered TiO₂ nanotubes were prepared by the electrochemical anodization of titanium in an ethylene glycol electrolyte containing 1 wt% NH₄F and 10 wt% H₂O at 20 V for 20 min, followed by annealing. The surface morphology and crystal structure of the samples were examined as a function of the annealing temperature by field emission scanning electron microscopy (FE‐SEM) and X‐ray diffraction (XRD), respectively. Crystallization of the nanotubes to the anatase phase occurred at 450 °C, while rutile formation was observed at 600 °C. Disintegration of the nanotubes was observed at 600 °C and the structure vanished completely at 750 °C. Electrochemical corrosion studies showed that the annealed nanotubes exhibited higher corrosion resistance than the as‐formed nanotubes. The growth of hydroxyapatite on the different TiO₂ nanotubes was also investigated by soaking them in simulated body fluid (SBF). The results indicated that the tubes annealed to a mixture of anatase and rutile was clearly more efficient than that in their amorphous or plain anatase state. The in vitro cell response in terms of cell morphology and proliferation was evaluated using osteoblast cells. The highest cell activity was observed on the TiO₂ nanotubes annealed at 600 °C. Copyright © 2010 John Wiley & Sons, Ltd.     

过渡金属氧化物和金属负载型沸石催化剂上合成 纳米碳管及其表征

采用气相催化沉积法催化合成纳米碳管,比较了不同金属氧化物和金属负载型沸石催化剂以及不同分子筛载体对合成纳米碳管的影响,并用TEM,XRD表征其形貌和结晶度,用DTA-TG考察了纳米碳管的热和稳定性。实验结果表明纳米碳管的形成除了与金属种类有关外,还直接与催化剂的颗粒大小和分散状态有关。粒径在20nm左右的不规则形状的纳米粒子是形成纳米碳管的活性组分,非负载和负载型的催化剂均表明活性组分的粒径与纳米碳管的管径有一定的对应关系。化学提纯后能得到高纯度的纳米碳管;其管壁具有较好的石墨化结构,在空气中的热稳定性大于400℃,而在氮气中能维持到1200℃以上。     

Polyurethane–oligo(phenylenevinylene) random copolymers: π‐Conjugated pores,vesicles, and nanospheres via solvent‐induced self‐organization

We report a new series of polyurethane–oligo(phenylenevinylene) (OPV) random copolymers and their self‐assembled nanomaterials such as pores, vesicles, and luminescent spheres. The polymers were synthesized through melt transurethane process by reacting a hydroxyl‐functionalized OPV with diurethane monomer and diol under solvent‐free and nonisocyanate conditions. The amount of OPV was varied up to 50 mol % in the feed to incorporate various amounts of π‐conjugated segments in the polyurethane backbone. The π‐conjugated segmented polymers were subjected to solvent induced self‐organization in THF or THF+water to produce variety of morphologies ranging from pores (500 nm to 1 μm) to spheres (100 nm to 2 μm). Upon shining 370‐nm light, the dark solid nanospheres of the copolymers transformed into blue luminescent nanoballs under fluorescence microscope. The mechanistic aspects of the self‐organization process were studied using solution FTIR and photophysical techniques such as absorption and emission to trace the factors which control the morphology. FTIR studies revealed that the hydrogen bonding plays a significant role in the copolymers with lower amount of OPV units. Time resolved fluorescent decay measurements of copolymers revealed that molecular aggregation via π‐conjugated segments play a major role in the samples with higher OPV content in the random block polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 46: 5897–5915, 2008     

Electrochemical deposition of poly[ethylene-dioxythiophene] (PEDOT) films on ITO electrodes for organic photovoltaic cells: control of morphology,thickness, and electronic properties

In this article, controlled changes on morphology, thickness, and band gap of poly[ethylenedioxythiophene] (PEDOT) polymer films fabricated by electrochemical polymerization (potentiostatically) are analyzed. Electropolymerization of the monomer ethylenedioxythiophene (EDOT) was carried out on indium tin oxide (ITO) electrodes, in different dry organic electrolytic media, such as acetonitrile, acetonitrile–dichloromethane, and toluene–acetonitrile mixtures. It was found that electropolymerization kinetics can be controlled by changing the polarity of the electrolytic media, and kinetics is slower for those with low polarity. This fact combined with an accurate control of EDOT monomer concentration and electropolymerization at E_peak/2 potential, allows to control the morphology and thickness of the electropolymerized PEDOT films (E-PEDOT:ClO₄); toluene/ACN (4:1, v/v) and [EDOT]?=?0.3 mM gave the best films for application in organic photovoltaic (OPV) cells. The performance of the E-PEDOT:ClO₄ films was tested on ITO electrodes as anode buffer layer in OPV cells with the configuration ITO/E-PEDOT:ClO₄/P3HT:PC₆₁BM/Field’s metal, where Field’s metal (cathode) is a eutectic alloy that lets to fabricate OPV devices easily and in a fast and economical way at free vacuum conditions. The performance of these devices was compared with an OPV device constructed with a buffer layer anode, prepared using the classical spin coating of PEDOT:PSS on ITO. Results showed that OPV cells fabricated with E-PEDOT:ClO₄ have a slightly increased PV performance.     

La~2NiO~4催化制备纳米碳管

制备了四方结构复合氧化物La~2NiO~4,并以其为催化剂前体,甲烷和一氧化碳为碳,合成出大量高纯度的纳米碳管。XRD结果表明La~2NiO~4经还原后,在La~2O~3的隔离作用下Ni晶粒实现纳米级均匀分散。利用TEM,HRTEM,SEM,XRD,Raman等手段对所制备的纳米碳管进行了观察和表征。所制备的纳米碳管管径均匀、石墨化程度较高,该法制备纳米碳管工艺简单、产量较高,产品易于纯化。     

以介孔分子筛为金属催化剂载体制备纳米碳管

 以不同的介孔分子筛作为金属催化剂载体,对催化合成纳米碳管进行了系统的研究,讨论了反应条件对纳米碳管纯度和产量的影响. 结果表明,不同的介孔分子筛对金属活性中心的形成、碳组分的扩散、纳米碳管的管径及形态均有明显的影响. 此外,金属的种类、状态和含量也影响纳米碳管的合成. 探索了合成高产量纳米碳管的条件,并对介孔分子筛上生长纳米碳管的特点进行了讨论.     

Self‐assembly of oligo(p‐phenylenevinylene)‐block‐poly(ethylene oxide) in polar media and solubilization of an oligo(p‐phenylenevinylene) homooligomer inside the assembly

Rod–coil amphiphilic diblock copolymers, consisting of oligo(p‐phenylenevinylene) (OPV) as a rod and hydrophobic block and poly(ethylene oxide) (PEO) as a coil and hydrophilic block, were synthesized by a convergent method. The aggregation behavior of the block copolymers in a selective solvent (tetrahydrofuran/H₂O) was probed with the absorption and emission of the OPV block. With increasing H₂O concentration, the absorption maximum was blueshifted, the emission from the molecularly dissolved OPV decreased, and that from the aggregated OPV increased. This indicated that the OPV blocks formed H‐type aggregates in which the OPV blocks aligned in a parallel orientation with one another. The transmission electron microscopy observation revealed that the block copolymers with PEO weight fractions of 41 and 62 wt % formed cylindrical aggregates with a diameter of 6–8 nm and a length of several hundreds nanometers, whereas the block copolymer with 79 wt % PEO formed distorted spherical aggregates with an average diameter of 13 nm. Furthermore, the solubilization of an OPV homooligomer with the block copolymer was studied. When the total polymer concentration was less than 0.1 wt %, the block copolymer solubilized OPV with a 50 mol % concentration. The structure of the aggregates was a cylinder with a relatively large diameter distribution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1569–1578, 2005     

Intense Ground‐State Charge‐Transfer Interactions in Low‐Bandgap,Panchromatic Phthalocyanine–Tetracyanobuta‐1,3‐diene Conjugates

A cycloaddition–retroelectrocyclization reaction between tetracyanoethylene and two zinc phthalocyanines (Zn^IIPcs) bearing one or four anilino‐substituted alkynes has been used to install a strong, electron‐accepting tetracyanobuta‐1,3‐diene (TCBD) between the electron‐rich Zn^IIPc and aniline moieties. A combination of photophysical, electrochemical, and spectroelectrochemical investigations with the Zn^IIPc‐TCBD‐aniline conjugates, which present panchromatic absorptions in the visible region extending all the way to the near infrared, show that the formal replacement of the triple bond by TCBD has a dramatic effect on their ground‐ and excited‐state features. In particular, the formation of extremely intense, ground‐state charge‐transfer interactions between Zn^IIPc and the electron‐accepting TCBD were observed, something unprecedented not only in Pc chemistry but also in TCBD‐based porphyrinoid systems.     

Positive Temperature Coefficient Characteristics of Multi-walled Carbon Nanotube Filled Polyvinylidene Fluoride Nanocomposites

Composites of polyvinylidene fluoride (PVDF) and multi-wall carbon nanotubes (MWNT) were prepared by a melt mixing process. Temperature dependence of electrical properties of the nanocomposites was investigated for composites containing different amounts of MWNT. An obvious positive temperature coefficient was observed. It was found that resistivity of the composites was decreased with increasing MWNT content and the electrical percolation threshold was formed at 3 wt% MWNT, which were caused by the formation of conductive chains in the composites. The mechanism of the positive temperature coefficient behavior of the nanocomposites is discussed. The rheological results showed that the materials experience a fluid–solid transition at the composition of 2 wt%, beyond which a continuous MWNT network forms throughout the matrix leading to a percolated network structure, which further indictes the nanotubes were dispersed uniformaly, in the PVDF matrix.     

EuF3 nanotubes fabricated via Eu(NO3)3/cysteamine as precursor and their derived thermosensitive nanogels

In this paper, we report a novel solution route to obtain rare earth nanotubes. Firstly, the complex of Eu(NO₃)₃/cysteamine (Eu-Complex) was used as the precursor, then nanotubes of EuF₃ were fabricated from the precursor and NaF. Secondly, the EuF₃ nanotubes reacted with acrylic acid (AA) and converted into vinyl decorated nanotubes. Finally, the decorated nanotubes copolymerized with N-isopropylacrylamide via free radical polymerization and thermosensitive EuF₃ nanotubes/poly (N-isopropylacrylamide) (PNIPAm) nanogels were prepared. In order to investigate the mechanism to produce the nanotubes, the morphology structures of samples at different reaction stages were studied via TEM, and the formation mechanism of nanotubes is proposed. The chemical composition was confirmed by FTIR, XRD, XPS and elemental analyzer. The optical property of the as-prepared nanotubes and the nanogels was investigated in detail by photoluminescence (PL). The results suggest that, compared with their bulk counterparts, the nanogels present different thermosensitive fluorescence behavior, for instance, around their low critical solution temperature (LCST), the variation of PL emission intensity of the nanogels is slightly gentler.     

Highly emissive supramolecular oligo(p-phenylene vinylene) dendrimers

pi-Conjugated oligo(p-phenylene vinylene) (OPV) guest molecules for interaction with dendritic hosts were synthesized and fully characterized by NMR spectroscopy, MALDI-TOF-MS, elemental analysis and optical measurements. The binding properties of the five different OPV guests to a N,N-bis[(3-adamantyl ureido) propyl] methylamine host have been investigated. The guests that contained an aryl urea glycine spacer were bound with the highest association constant. Subsequently, an adamantyl urea modified fifth generation poly(propylene imine) dendrimer was synthesized as a multivalent host which contains 32 N,N-bis[(3-adamantyl ureido) propyl] amine binding sites. Size exclusion chromatography showed that 32 of the OPV guests strongly bind to the fifth generation adamantyl functionalized dendritic host. In the case of the supramolecular dendritic host/guest system smooth homogeneous thin films could be obtained by spin coating. The dendritic guest-host complexes showed a significantly higher emission upon binding then that of the individual molecules due to the three-dimensional orientation of the OPV guest molecules. In the solid state, this enhancement in luminescence was a factor of 10. The pi-conjugated oligomers are less aggregated in the supramolecular assemblies presumably because of a shielding effect of the bulky adamantyl units present in the hosts.     

Length-controlled rodlike self-assemblies in binary mixed langmuir-blodgett monolayers on mica

In this paper, atomic force microscopy (AFM) has been used to investigate the morphology of monolayers of the amphiphilic rod-coil diblock molecule (EO7OPV) containing oligo(phenylene vinylene) dimer (OPV) and poly(ethylene oxide) (PEO) as well as the morphology of mixed monolayers of EO7OPV and palmitic acid (PA) deposited onto mica by the Langmuir-Blodgett technique. At surface pressures higher than 3 mN/m, EO7OPV forms regular-shaped aggregates with a monomolecular layer structure, where the hydrophilic PEO blocks are adsorbed onto the mica substrate and the hydrophobic OPV blocks form an ordered crystalline OPV layer on the top of the PEO layer through the strong pi-pi stacking interaction. In the mixed LB monolayers of EO7OPV and PA, the phase separation occurs. At a certain mixed ratio, EO7OPV molecules form rodlike domains with regular shape and uniform size at surface pressures higher than 3 mN/m. With the increase of the molar fraction of PA, the rodlike domains consisting of EO7OPV are elongated. The length of the rodlike domains can be tuned easily in a large range by altering the molar ratio of EO7OPV and PA. In addition, the rodlike domains are oriented to specific directions, corresponding to the directions of the potassium ion array on the mica surface having 6-fold symmetry. We demonstrate the possible formation mechanism and the elongation origin of rodlike domains in mixed LB monolayers and propose the two-step formation process of oriented rodlike domains deposited onto the mica substrate.