Photoinduced electron transfer reaction tuned by donor-acceptor pairs via the rigid, linear spacer heptacyclo[6.6.0.0.0.0.0.0]tetradecane

A new class of donor-{saturated hydrocarbon bridge}-acceptor (D-B-A) dyads were synthesized and utilized on a systematic approach to evaluate the corresponding photoinduced electron transfer (ET) process. Among these dyads heptacyclo[6.6.0.0^2,6.0^3,13.0^4,11. 0^5,9.0^10,14]tetradecane (HCTD) was used as a unique spacer, which possesses a geometry of high symmetry (D_2d), rigidity and linearity. The spectroscopy and dynamics of excited-state ET as functions of donor/acceptor electronic states, orientation as well as solvent properties were analyzed with the aid of theoretical computations. It was observed that the quenching of donor fluorescence (the F₁ band) correlated with the appearance of a broad charge-transfer (CT) emission. Both wavelength and intensity of the CT band varied with solvent-polarity, whereas its rise dynamics complied well with the decay of the F₁ band. In acetonitrile, the CT state decays much faster than the rate of ET (∼63 ps⁻¹) so that the corresponding steady-state emission cannot be resolved. An intriguing effect was observed in the case of benzene-1,2-dithioketals (3a and 3b) where the D and A π-chromophores were aligned in different orientations. The estimated ET rate of 3a (3.9×10¹⁰ s⁻¹) was substantially faster than that of 3b (7×10⁸ s⁻¹). The experimental data were tentatively fitted by a semi-log plot of ET rate constants (k_et) against free energy (ΔG⁰), yielding a value of ∼17.3 cm⁻¹ for the electron-coupling matrix (H_el).     

Thermotropic copolyesters having ordered comonomer sequences and flexible spacers

A series of new copolyesters having ordered comonomer sequences were synthesized via multistep routes and their properties such as glass transition (T_g) and melting temperatures (T_m), crystallization tendency, and mesomorphic properties were compared with those of the corresponding random copolyesters. All of the present copolyesters contain 1,8-octamethylene or 1,10-decamethylene spacers and hydroquinone (HQ) and terephthalic acid (TPA) moieties. In general, both melting and clearing temperatures of the ordered sequence copolyesters were much higher than those of the random counterparts. Crystallization tendency, however, was comparable. All of the present copolyesters are thermotropic and form nematic phase in melts. © 1993 John Wiley & Sons, Inc.     

Effect of the poly(oxytetramethylene)diol spacer length on some properties of liquid crystalline polyurethanes

Previous studies on liquid crystalline polyurethanes prepared from 4,4′-bis(2-hydroxyethoxy)biphenyl (BHBP) and 2,4-tolylene diisocyanate (TDI) were continued. In this article, a series of polyurethanes, which differ in the flexible spacer length and BHBP content is described. Poly(oxytetramethylene)diols of different molecular weights (PTMO, M _n = 250, 650, 1000, 2000) were used as flexible spacers. The polyurethanes were investigated by DSC, polarizing microscopy, x-ray diffractometry, and IR spectroscopy. The molecular weight distribution was determined by GPC. The morphology of the polyurethanes was investigated by the SALS method. Partial replacement of BHBP by 25–75 mol % PTMO and the flexible spacer length influence the liquid crystalline properties, the phase transition temperatures, and the range of mesophase occurrence. © 1993 John Wiley & Sons, Inc.     

Surface chemistry of selected supported metallocene catalysts studied by DR‐FTIR,CPMAS NMR,and XPS techniques

Two supported metallocene catalysts (CS 1: PQ 3030/MAO/Cp₂ZrCl₂ and CS 2: PQ 3030‐BuGeCl₃/MAO/Cp₂ ZrCl₂) were prepared by sequentially loading MAO and Cp₂ZrCl₂ on partially dehydroxylated silica PQ 3030. In catalyst CS 2, ⁿBuGeCl₃ was used to functionalize the silica. These catalysts were characterized by DR‐FTIR spectroscopy, CPMAS NMR spectroscopy, and XPS. Their catalytic performance was evaluated by polymerizing ethylene using the MAO cocatalyst and characterizing the resulting polymers by GPC. Both catalysts produced two metallocenium cations (Cation 1: [Cp₂ZrCl]⁺ and Cation 2: [Cp₂ZrMe]⁺) with comparable equilibrium concentrations and showed varying solid‐state electronic environments. The modified supports (PQ 3030/MAO and PQ 3030‐BuGeCl₃/MAO) acted as weakly coordinating polyanions and stabilized the above cations. BuGeCl₃ did not affect the solid‐state electronic environment. However, it increased the surface cocatalyst to catalyst molar ratio (Al:Zr), acted as a spacer, increased catalyst activity, and enhanced chain‐transfer reactions. The separately fed MAO cocatalyst shifted the equilibrium between Cation 1 and Cation 2 toward the right. Consequently, more Cation 2 was generated, which acted as the effective and active single‐site catalytic species producing monomodal PDI. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis and polymerization of 1-(2,4,6-tricyanophenylthio)-3-[3,5-bis(n,n-dimethylamino)phenoxy]-2-propyl methacrylate; polymer effect on intramolecular charge–transfer interaction

1-[3,5-Bis(N,N-dimethylamino)phenoxy]-ω-(2,4,6-tricyanophenylthio)alkanes ( 1a–c ), where an electron-accepting 2,4,6-tricyanophenylthio group and an electron-donating 3,5-bis(N,N-dimethylamino)phenoxy one are linked with a spacer such as ethylene, trimethylene, and tetramethylene, were prepared in order to examine an effect of the spacer chain length on intramolecular charge–transfer interaction between the 2,4,6-tricyanophenylthio and 3,5-bis(N,N-dimethylamino)phenoxy groups. From the UV-vis spectra measurements of 1a–c , 1-[3,5-bis(N,N-dimethylamino)phenoxy]-3-(2,4,6-tricyanophenylthio)Propane ( 1b ) carrying the trimethylene chain as a spacer was found to have the strongest intramolecular charge–transfer interaction. A new methacrylate-type monomer carrying the 1b unit as a side chain, 1-(2,4,6-tricyanophenylthio)-3-[3,5-bis(N,N-dimethylamino)phenoxy]-2-propyl methacrylate ( 2 ), was prepared successfully in 9.2% total yield in seven steps. The monomer 2 homopolymerized in benzene, tetrahydrofuran, acetone, and dimethyl sulfoxide in the presence of 2,2′-azobis(isobutyronitrile) at 60°C to give polymers [poly( 2 )] with molecular weights of 6,000 to 98,000. An intramolecular charge–transfer interaction in the poly( 2 ) was found to be larger than that in the monomer 2 and to increase with an increase in the degree of polymerization of the poly( 2 ), suggesting that there is an existence of polymer effect other than the polymer effect due to the high local concentration of the donor-acceptor pair. © 1995 John Wiley & Sons, Inc.     

Synthesis and chiroptical properties of optically active polymer liquid crystals containing azobenzene chromophores

A series of optically active methacrylic homopolymers, poly[(4‐{4′‐[(S)‐2‐methyl‐1‐butyloxycarbonyl]phenylazo}phenoxyl)x‐methylene methacrylate] (x = 0, 2, 6, or 11), were synthesized. The structures of the polymers were characterized by IR, ¹H NMR, UV, differential scanning calorimetry, and gel permeation chromatography. The chiroptical properties of the polymers in films were investigated with circular dichroism (CD) measurements. The CD and UV spectra of the films suggested that CD absorptions occurred in the films of the polymers with long spacers (x = 6 or 11) but not in the films of the polymers with short spacers (x = 0 or 2). After irradiation with linearly polarized light at 442 nm, the CD values were amplified in all the polymeric films. The amplificatory values of the CD bands in the absorption region (260–360 nm) of azobenzene chromophores suggested that the spacer length had an effect on both the transfer of chirality and photoinduced chirality in the polymeric films. The largest level of photoinduced chirality was induced in the polymer containing six methylene units. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3210–3219, 2006     

Single-electron transistors fabricated with sidewall spacer patterning

We have implemented a sidewall spacer patterning method for novel dual-gate single-electron transistor (DGSET) and metal–oxide–semiconductor-based SET (MOSET) based on the uniform SOI wire, using conventional lithography and processing technology. A 30 nm wide silicon quantum wire is defined by a sidewall spacer patterning method, and depletion gates for two tunnel junctions of the DGSET are formed by the doped polycrystalline silicon sidewall. The fabricated DGSET and MOSET show clear single-electron tunneling phenomena at liquid nitrogen temperature and insensitivity of the Coulomb oscillation period to gate bias conditions. On the basis of the phase control capability of the sidewall depletion gates, we have proposed a complementary self-biasing method, which enables the SET/CMOS hybrid multi-valued logic (MVL) to operate perfectly well at high temperature, where the peak-to-valley current ratio of Coulomb oscillation severely decreases. The suggested scheme is evaluated by SPICE simulation with an analytical DGSET model, and it is confirmed that even DGSETs with a large Si island can be utilized efficiently in the multi-valued logic.     

Matrix Projection Exposure Using an Analogue Liquid Crystal Display Panel in Place of a Reticle

The most serious problems for the matrix projection exposure using a liquid crystal display (LCD) panel in place of a reticle are largely solved by a new breakthrough method. LCD matrix exposure is effective for small volume productions of print circuits, screen masks, micromachine parts, and other items. Since no reticles are needed, all reticle costs are saved, and turnaround times required for changing the patterns are greatly shortened. However, in the conventional method, pattern widths and positions were strictly restricted depending on the geometric size and pitch of the liquid crystal cells. In this paper, a new concept appointing the cell brightness grades continuously using an analogue interface LCD panel is proposed. Calculating the image intensity distributions for various appointments of cell brightness balances to print same wide patterns, it is clarified that the pattern widths and positions are not much different if the pattern widths are wider than 2 cell pitches of the LCD panel. Maximum width and position variations are less than ± 10% even when the patterns are printed at arbitrary positions, of course including halfway ones. The calculated results are proved by experiments using an analogue LCD panel with a cell pitch of 15 μm. Though the cell size are 13 × 10 μm², and different in x and y directions, almost same wide line-and-space patterns are successfully printed at all positions by only one exposure. It is not necessary to shift the reticle for overlapping exposures to print smooth patterns. Oblique patterns and complicated Chinese character patterns are also printed at arbitrary positions. The new breakthrough technology will make the LCD matrix exposure promising for wide uses of printing various rough patterns easily at small costs.     

低温液晶显示器—加固理论与实践

该文对液晶显示器(LCD)低温加固的理论进行分析和研究。在此基础上,介绍一种新研制的机载低温液晶显示器。在显示器中设计了一套透明的加热、真空保温、抗眩光及电磁屏蔽装置,低温工作时,只需非常小的加热功率,就能使液晶显示器正常工作,同时可以利用该装置中的氧化铟锡(ITO)导电膜层满足显示器视窗对防眩光及电磁兼容(EMC)特性的要求。这种新型低温加固型LCD集多种特殊功能于一体,具有功耗低、亮度高、可靠性好、抗眩光、EMC性能好及结构便于组装等多项显著优点。     

液晶显示器颜色特征化的分段分空间模型

为了提高液晶显示器(LCD)颜色特征化精度,根据液晶显示器色品恒定性和通道独立性较差的特点,提出了分段分空间模型。该模型首先用分段二次多项式拟合单通道驱动值和三刺激值的关系,然后再根据不同RGB子空间的颜色特性加上适当的干扰项对液晶显示器进行颜色特征化。实验结果表明,在训练样本和检验样本数分别为91和512时分段分空间模型的CIELAB平均色差为1.5881,最大色差为6.0249;通过与三维查找表、Mask、S-Curve及TPC模型的比较研究,验证了当训练样本数不多时分段分空间模型的颜色预测精度最高。