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1.
Chesney A Bryce MR Yoshida S Perepichka IF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(7):1153-1159
Two conceptually different routes to transient 1,2-diselones are reported: 1) via ring fragmentation of the 1,4,2-diselenazine system 6, and 2) by the tributylphosphane-induced depolymerisation of the shelf-stable organoselenium polymer 15. Evidence for the intermediacy of 1,2-diselone species 7 and 16 is provided in both cases by in situ trapping with dimethyl acetylenedicarboxylate (DMAD) to yield 1,4-diselenin derivatives. The route via 15 is especially expedient and trapping of 16 is efficient. Subsequent reactions of adduct 17 afford [1,2-ethanediylbis(diphenylphosphane)] [5,6-bis(methoxycarbonyl)-1,4-diselenin-2,3-dithiolato]nickel(IV) (20). Theoretical calculations at Hartree-Fock (HF) and Moller-Plesset electron-correlated levels (MP2) suggest that the cyclic 1,2-diselenete structure 7c is significantly more stable than the acyclic 1,2-diselone structure 7a. For the bicyclic system 16, the difference in energy between the cyclic and acyclic structures is considerably reduced due to the conformational rigidity imposed by the fused 1,3-dithiole ring. In contrast, the acyclic structures of the 1,2-dithione analogues 13a and 25a are computed to be more stable than their corresponding cyclic 1,2-dithiete structures 13c and 25c. 相似文献
2.
Svetlana B. Lyubchik Irene I. Perepichka Olga L. Galushko Andrey I. Lyubchik Elena S. Lygina Isabel M. Fonseca 《Adsorption》2005,11(5-6):581-593
In order to understand the patterns of the adsorption equilibrium of Cr (III) on activated carbon, the adsorption process
was studied by two different ways: classical batch experiments on commercial Norit and Merck activated carbons and their oxidized
forms in a wide range of pHs; and extended time-based tests at the same pH values on the same adsorbents. This approach allowed
us to understand the role of texture, chemical carbon surface functionality and experimental conditions (initial pH of the
solution, contact time and adsorbate/adsorbent ratio) on the effectiveness of Cr (III) removal. The adsorption process of
Cr (III) at (24 ± 1∘C) on Merck and Norit activated carbons and their oxidized forms were studied at pH values between 1.5 and 5 (either adjusted
or buffered). Chromium concentration was fixed at 200 ppm. The carbon loading ranged from 1.2 to 20 g/l. The carbon/Cr (III)
solution contact time was varied from 0.5–1 month to 5 months, to ensure that the saturation of the carbon level was reached.
According to the data obtained, the presence of carboxylic groups on carbon surface seems to enhance Cr (III) uptake at initial
pH of the solution in the range between 2 and 4. Depending on the nature of the adsorbent surface chemistry, the contact time
to reach equilibrium may range from 3 to 5 months. There is an optimum carbon loading which limits the Cr (III) uptake/removal
at given pH value. In order to understand the adsorption process, an ion exchange, surface complex and surface precipitation
were considered.
This paper was presented in the 5th Brazilian Meeting on Adsorption, held at Natal, Brazil, 18-21 July, 2004. 相似文献
3.
Synthesis and properties of monodisperse oligofluorene-functionalized truxenes: highly fluorescent star-shaped architectures 总被引:2,自引:0,他引:2
Kanibolotsky AL Berridge R Skabara PJ Perepichka IF Bradley DD Koeberg M 《Journal of the American Chemical Society》2004,126(42):13695-13702
This paper describes the strategy toward novel monodisperse, well-defined, star-shaped oligofluorenes with a central truxene core and from monofluorene to quaterfluorene arms. Introduction of solubilizing n-hexyl groups at both fluorene and truxene moieties results in highly soluble, intrinsically two-dimensional nanosized macromolecules T1-T4. The radius for the largest oligomer of ca. 3.9 nm represents one of the largest known star-shaped conjugated systems. Cyclic voltammetry experiments reveal reversible or quasi-reversible oxidation and reduction processes (Eox = +0.74 to 0.80 V, Ered = -2.66 to 2.80 eV vs Fc/Fc+), demonstrating excellent electrochemical stability toward both p- and n-doping, while the band gaps of the oligomers are quite high (EgCV = 3.20-3.40 eV). Close band gaps of 3.05-3.29 eV have been estimated from the electron absorption spectra. These star-shaped macromolecules demonstrate good thermal stability (up to 400-420 degrees C) and improved glass transition temperatures with an increase in length of the oligofluorene arms (from Tg = 63 degrees C for T1 to 116 degrees C for T4) and show very efficient blue photoluminescence (lambdaPL = 398-422 nm) in both solution (PhiPL = 70-86%) and solid state (PhiPL = 43-60%). Spectroelectrochemical experiments reveal that compounds T1-T4 are stable electrochromic systems which change their color reversibly from colorless in the neutral state (approximately 340-400 nm) to colored (from red to purple color; approximately 500-600 nm) in the oxidized state. 相似文献
4.
Solid-state synthesis of a conducting polythiophene via an unprecedented heterocyclic coupling reaction 总被引:2,自引:0,他引:2
Meng H Perepichka DF Bendikov M Wudl F Pan GZ Yu W Dong W Brown S 《Journal of the American Chemical Society》2003,125(49):15151-15162
Prolonged storage ( approximately 2 years) or gentle heating (50-80 degrees C) of crystalline 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) affords a highly conducting, bromine-doped poly(3,4-ethylenedioxythiophene) (PEDOT), as confirmed by solid-state NMR, FTIR, CV, and vis-NIR spectroscopies. The novel solid-state polymerization (SSP) does not occur for 2,5-dichloro-3,4-ethylenedioxythiophene (DCEDOT), and requires a much higher temperature (>130 degrees C) for 2,5-diiodo-3,4-ethylenedioxythiophene (DIEDOT). X-ray structural analysis of the above dihalothiophenes reveals short Hal.Hal distances between adjacent molecules in DBEDOT and DIEDOT, but not in DCEDOT. The polymerization may also occur in the melt but is significantly slower and leads to poorly conductive material. Detailed studies of the reaction were performed using ESR, DSC, microscopy, and gravimetric analyses. SSP starts on crystal defect sites; it is exothermic by 14 kcal/mol and requires activation energy of approximately 26 kcal/mol (for DBEDOT). The temperature dependence of the conductivity of SSP-PEDOT (sigma(rt) = 20-80 S/cm) reveals a slight thermal activation. It can be further increased by a factor of 2 by doping with iodine. Using this approach, thin films of PEDOT with conductivity as high as 20 S/cm were fabricated on insulating flexible plastic surfaces. 相似文献
5.
Perepichka IF Popov AF Orekhova TV Bryce MR Andrievskii AM Batsanov AS Howard JA Sokolov NI 《The Journal of organic chemistry》2000,65(10):3053-3063
2,4,5,7-Tetranitro-9-fluorenone (1b) reacts readily with n-butanethiol in dipolar aprotic solvents with selective substitution of nitro groups by butylsulfanyl groups in positions 2 and 7 (2, 3); the 2,5-isomer 4 was formed only as a minor product (<1%). Condensation of fluorenones 2-4 with malononitrile yielded 9-dicyanomethylene derivatives 5-7, which showed strong intramolecular charge transfer (lambda approximately 510-560 nm) and were found to sensitize the photoconductivity of carbazole-containing polymer films. Oxidation of sulfides 2-4 gave sulfoxide 8 or sulfones 9-11, which then were converted into their corresponding dicyanomethylene derivatives 12-15. All these novel acceptors showed three reversible single-electron reduction waves (cyclic voltammetry) yielding radical anion, dianion, and radical trianion; moreover, acceptors 13-15 showed also a fourth reduction wave, representing reversible tetraanion formation. Substitution of the oxygen of the carbonyl group in the fluorenones by a dicyanomethylene group increased the thermodynamic stability (K(SEM) growth) of the radical anion; K(SEM) ranged from 3 x 10(5) to 3 x 10(9) M(-1). CV measurements characterize compounds 3, 4 (EA = 1. 86-1.89 eV) as poor acceptors, 2, 6-11 (EA = 2.13-2.31 eV) as moderate acceptors, and 5, 12-15 (EA = 2.53-2.66 eV) as strong electron acceptors. Charge-transfer complex (CTC) formation between acceptors 9, 10, 13, 14, and anthracene as a donor was monitored by the appearance of additional low-energy bands in the visible region (CTC bands) of their electron absorption spectra. Increasing the EA of the acceptors from 9-fluorenones to the corresponding 9-dicyanomethylenefluorenes increases the complexation constants K(CTC) by 2.5-3 times, while sulfonyl substituents present substantial steric hindrance for complexation (as compared to the nitro group), decreasing K(CTC) values. Two CTCs for acceptors 14 and 17 with tetrathiafulvalene (TTF) were obtained, and their structures were solved by single-crystal X-ray diffractometry, giving the stoichometries 14:TTF, 2:3, and 17:TTF:PhCl, 1:1:0.5. In the former complex the packing motif is a mixed.DDAD'A. stack; in the latter complex the D and A moieties form unusually close CT pairs, which pack in a herringbone motif. 相似文献
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Mengmeng Zhu Weishuo Li Panpan Xu Jingjing Shi Shan Shao Xiaosi Zhu Yitong Guo Yaowu He Zhao Hu Hongtao Yu Yanan Zhu Igor F. Perepichka Hong Meng 《中国科学:化学(英文版)》2017,60(1):63-76
Thieno[3,2-b]thiophene (TT) monomers end-capped with 3,4-ethylenedioxythiophene (EDOT) moieties are electropolymerized to form π-conjugated polymers with distinct electrochromic (EC) properties. Steric and electronic factors (electron donor and acceptor substituents) in the side groups of the TT core, as well as the structure of the polymer backbone strongly affect the electrochemical and optical properties of the polymers and their electrochromic characteristics. The studied polymers show low oxidation potentials, tunable from–0.78 to +0.30 V (vs. Fc/Fc+) and the band gaps from 1.46 to 1.92 eV and demonstrate wide variety of color palettes in polymer films in different states, finely tunable by structural variations in the polymer backbone and the side chains. EC materials of different colors in their doped/dedoped states have been developed (violet, deep blue, light blue, green, brown, purple-red, pinkish-red, orange-red, light gray, cyan and colorless transparent). High optical contrast (up to 79%), short response time (0.57–0.80 s), good cycling stability (up to 91% at 2000 cycles) and high coloration efficiency (up to 234.6 cm2 C–1) have been demonstrated and the influence of different factors on the above parameters of EC polymers have been discussed. 相似文献
9.
Perepichka II Perepichka IF Bryce MR Pålsson LO 《Chemical communications (Cambridge, England)》2005,(27):3397-3399
Incorporation of dibenzothiophene-S,S-dioxide units into conjugated fluorene oligomers changes the frontier orbital energy levels and presents an effective way to increase the electron affinity of these materials, which are highly fluorescent with bright blue emission in both solution and the solid state. 相似文献
10.
Thaksen Jadhav Yuan Fang William Patterson Cheng‐Hao Liu Ehsan Hamzehpoor Dmitrii F. Perepichka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(39):13891-13895
Designing structural order in electronically active organic solids remains a great challenge in the field of materials chemistry. Now, 2D poly(arylene vinylene)s prepared as highly crystalline covalent organic frameworks (COFs) by base‐catalyzed aldol condensation of trimethyltriazine with aromatic dialdehydes are reported. The synthesized polymers are highly emissive (quantum yield of up to 50 %), as commonly observed in their 1D analogues poly(phenylene vinylene)s. The inherent well‐defined porosity (surface area ca. 1000 m2 g?1, pore diameter ca. 11 Å for the terephthaldehyde derived COF‐1) and 2D structure of these COFs also present a new set of properties and are likely responsible for the emission color, which is sensitive to the environment. COF‐1 is highly hydrophilic and reveals a dramatic macroscopic structural reorganization that has not been previously observed in framework materials. 相似文献