Gold nanoparticle-templated assembly of oligothiophenes: preparation and film properties

Terthiophene-appended gold nanoparticles were prepared by the reduction of AuCl₄⁻(C₈H₁₇)₄N⁺ with NaBH₄ in the presence of bis[2,5-di(3-hexylthiophen-2-yl)thiophene-3-carboxyloxyhexanyl]disulfide. A hexagonal self-assembly of particles with gold core diameters (1.9±0.1 nm) was detected by high-angle annular dark-field scanning transmission electron microscopy. The electric conductivity of the iodine-doped film was 9.1×10⁻⁶ S cm⁻¹, which was ascribable to the terthiophene-based inter-ligand π-π interactions. The Au/terthiophene hybrid spin-coated film consisted of a highly three-dimensional assembled structure of terthiophenes, as inferred from grazing-incidence small-angle X-ray scattering, indicating that such monodispersed and small-sized gold nanoparticles can serve as a template for this organization. In this study, a gold nanoparticle-templated assembly of oligothiophenes has been fabricated for proposing a method to develop tailor-made organizations of π-conjugated oligomers.     

Approaching the Integer-Charge Transfer Regime in Molecularly Doped Oligothiophenes by Efficient Decarboxylative Cross-Coupling

A library of symmetrical linear oligothiophene was prepared employing decarboxylative cross-coupling reaction as the key transformation. Thiophene potassium carboxylate salts were used as cross-coupling partners without the need of co-catalyst, base, or additives. This method demonstrates complete chemoselectivity and is a comprehensive greener approach compared to the existing methods. The modularity of this approach is demonstrated with the preparation of discreet oligothiophenes with up to 10 thiophene repeat units. Symmetrical oligothiophenes are prototypical organic semiconductors where their molecular electrical doping as a function of the chain length can be assessed spectroscopically. An oligothiophene critical length for integer charge transfer was observed to be 10 thiophene units, highlighting the potential use of discrete oligothiophenes as doped conduction or injection layers in organic electronics applications.     

Synthesis, optical, and electrochemical properties of conjugated oligomers derived from 4-bromo-4-(n-butyl)-2,2-biphenyl

The synthesis, optical, and electrochemical properties of semi-conducting co-oligomers of biphenyl/oligothiophenes and homo-oligophenylenes derived from a precursor 4-bromo-4^′-(n-butyl)-2,2^′-biphenyl, which was synthesized by a direct alkylation from 4,4^′-dibromo-2,2^′-biphenyl using n-butyl lithium, are reported.     

Absorbance spectra of polycrystalline samples and twinned crystals of oligothiophenes

We propose optical absorption technique at oblique incidence as one of the spectroscopic tools that allow experimentally recognizing the macroscopic order and structural features of molecular solids of conjugated molecules, from single crystals to polycrystalline or twinned samples. We apply this spectroscopy to quaterthiophene as representative of a wide class of materials that usually possess optical transitions of Frenkel exciton origin with strong directional dispersion. The comparison between experimental and simulated data gives evidence of the high sensitivity of this technique for determining quantitatively the polycrystallinity of the measured samples, whose domains may show mirror-like orientation of the unit cell with respect to one of its faces.Frenkel exciton; Oligothiophene, Optical properties     

Synthesis, characterization, and properties of 7,7′-bis(3,6-di-tert-butylcarbazol-N-yl)-substituted fluorenyl-oligothiophenes

A series of new 7,7′bis(3,6-di-tert-butylcarbazol-N-yl)-substituted fluorenyl-oligothiophenes bearing 0-, 2-, 4-, 6-, and 8-thiophene rings, namely BCFTn, were synthesized using palladium catalyzed Stille dimerization coupling reactions of their corresponding brominated thiophenes. The relationship between the chemical structure and the properties of these oligomers was evaluated. With respect to the electronic properties, the longest wavelength absorptions, emissions, and also the oxidation potentials can be tuned by varying the conjugation length of the oligothiophene segments. The terminal carbazole and fluorene moieties of the resulting materials are beneficial for their morphology, conjugation length, and solubility.     

Symmetrical fluorescent oligothiophene and benzene centered bispyrenoimidazole derivatives with double n-dodecyl chains showing high thermal stability

A family of symmetrical oligothiophene (dithiophene, terthiophene, and quaterthiophene) or benzene centered bispyrenoimidazole derivatives, having the same coplanar pyrenoimidazole terminal groups at each side, has been synthesized via Radziszewski, N-alkylation, and the following Pd(PPh₃)₄ catalyzed Suzuki and Stille coupling reactions. Double n-dodecyl chains are introduced to the molecules at the same time in order to increase their solubility in organic solvents. UV–vis and fluorescence spectra as well as thermal properties have been studied. The results demonstrate that compound 4 with a benzene linker displays the strongest fluorescence intensity, and oligothiophene centered bispyrenoimidazole derivatives 5–7 show obvious bathochromic shifts compared with benzene centered compound 4. It is worth mentioning that this family of compounds exhibits excellent thermal stability with the decomposition temperature higher than 400 °C even if the incorporation of double n-dodecyl chains. Furthermore, X-ray single-crystal structures of one representative compound 4·(CHCl₃)₂ and an intermediate 3 have been described.     

Unusual thiophilic ring-opening of fused oligothiophenes with organolithium reagents

Organolithium reagents attack the sulfur atoms of fused oligothiophenes producing ring-opened organolithium intermediates that can be trapped with a suitable electrophile. The reaction was found to be general for fused thieno[2,3-b]-thiophenes and some [3,2-b]-fused oligothiophenes. Thermodynamic (organilithiums basicity) and mechanistic (RLi coordination by neighboring sulfur) aspects control the substrate scope and regioselectivity of the reaction. When competitive deprotonation of the substrate is possible, high selectivity toward ring-opening was observed with n-BuLi when compared with the other tested organolithiums. The recently discovered octathio[8]circulene produces multifold ring-opening products.     

Molecular engineering leading to better processability of conjugated chromophores: The optical properties of new soluble copolymers containing alternative oligo-octylthiophene and oligo-methylene blocks

A series of conjugated/non-conjugated copolymers and their corresponding oligomers were prepared and their optical and physical properties were investigated for understanding the merit of blocking the conjugated chromophores with non-conjugated spacers. It was found that compared to the oligomers, copolymers have the advantages of amorphous nature, high thermal stability, and good thin film processability without sacrificing the quantum efficiency and purity of the emission color. Furthermore, based on the optical data of these copolymers and oligomers, the conjugation length of the polyoctylthiophene was estimated to be extended over 23-31 octylthiophene rings.     

吡咯并吡咯二酮与低聚噻吩共聚物电荷传输性质的理论研究

利用密度泛函理论对吡咯并吡咯二酮(DPP)与噻吩形成共聚物的低聚物(PDPP-n T)m的电子结构及二体堆积模型的电荷传输性质进行计算.结果表明,随着聚合物单元内DPP浓度增加,噻吩数减少,聚合物分子的HOMO和LUMO能级同时降低,并且HOMO-LUMO带隙变小;链内相邻DPP单元的电子波函数有效重叠增大,显著改善了链内的电子传输能力;同时分子主链的刚性增强,使分子链间LUMO轨道重叠增强,电子转移积分增大;最终体系由p型向双极性材料转化.