Photoinduced processes within compact dyads based on triphenylpyridinium-functionalized bipyridyl complexes of ruthenium(II)

As an alternative to conventional charge-separation functional molecular models based on long-range ET within redox cascades, a "compact approach" has been examined. To this end, spacer elements usually inserted between main redox-active units within polyad systems have been removed, allowing extended rigidity but at the expense of enhanced intercomponent electronic communication. The molecular assemblies investigated here are of the P-(theta (1))-A type, where the theta (1) twist angle is related to the degree of conjugation between the photosensitizer (P, of {Ru(bpy)(3)}(2+) type) and the electron-acceptor (A). 4-N- and 4-N-,4'-N-(2,4,6-triphenylpyridinio)-2,2'-bipyridine ligands (A(1)-bpy and A(2)-bpy, respectively) have been synthesized to give complexes with Ru(II), 1-bpy and 2-bpy, respectively. Combined solid-state analysis (X-ray crystallography), solution studies ((1)H NMR, cyclic voltammetry) and computational structural optimization allowed verifying that theta (1) angle approaches 90 degrees within 1-bpy and 2-bpy in solution. Also, anticipated existence of strong intercomponent electronic coupling has been confirmed by investigating electronic absorption properties and electrochemical behavior of the compounds. The capability of 1-bpy and 2-bpy to undergo PET process was evaluated by carrying out their photophysical study (steady state emission and time-resolved spectroscopy at both 293 and 77 K). The conformational dependence of photoinduced processes within P-(theta (1))-A systems has been established by comparing the photophysical properties of 1-bpy (and 2-bpy) with those of an affiliated species reported in the literature, 1-phen. A complementary theoretical analysis (DFT) of the change of spin density distribution within model [1-bpy(theta (1))](-) mono-reduced species as a function of theta (1) has been undertaken and the possibility of conformationally switching emission properties of P was derived.     

Monolayer Rectifiers

Molecular-scale electronics has now been enriched by the discovery that molecules, studied singly by scanning tunneling spectroscopy, or a large array of those molecules, studied in parallel as a Langmuir-Blodgett monolayer between metal electrodes, exhibit rectification, i.e., an asymmetric current as a function of applied voltage.This asymmetry can come, first, from work function differences between two dissimilar metals or the metal-molecule interfaces (Schottky barriers), second from an asymmetric placement of the chromophore between the two metal electrodes, and third, from an asymmetry of the molecular orbitals of the molecule.This third, electronic origin of rectification, first proposed by Aviram and Ratner in 1974, and confirmed in the work reported here, gives us hope that, not too many years from now, molecules can form the basis of ultra-small yet ultra-fast electronic devices and integrated circuits.     

Controllable donor-acceptor neutral [2]rotaxanes

In pursuit of a neutral bistable [2]rotaxane made up of two tetraarylmethane stoppers--both carrying one isopropyl and two tert-butyl groups located at the para positions on each of three of the four aryl rings--known to permit the slippage of the pi-electron-donating 1,5-dinaphtho[38]crown-10 (1/5DNP38C10) at the thermodynamic instigation of pi-electron-accepting recognition sites, in this case, pyromellitic diimide (PmI) and 1,4,5,8-naphthalenetetracarboxylate diimide (NpI) units separated from each other along the rod section of the rotaxane's dumbbell component, and from the para positions of the fourth aryl group of the two stoppers by pentamethylene chains, a modular approach was employed in the synthesis of the dumbbell-shaped compound NpPmD, as well as of its two degenerate counterparts, one (PmPmD) which contains two PmI units and the other (NpNpD) which contains two NpI units. The bistable [2]rotaxane NpPmR, as well as its two degenerate analogues PmPmR and NpNpR, were obtained from the corresponding dumbbell-shaped compounds NpPmD, PmPmD, and NpNpD and 1/5DNP38C10 by slippage. Dynamic 1H NMR spectroscopy in CD2Cl2 revealed that shuttling of the 1/5DNP38C10 ring occurs in NpNpR and PmPmR, with activation barriers of 277 K of 14.0 and 10.9 kcal mol(-1), respectively, reflecting a much more pronounced donor-acceptor stabilizing interaction involving the NpI units over the PmI ones. The photophysical and electrochemical properties of the three neutral [2]rotaxanes and their dumbbell-shaped precursors have also been investigated in CH2Cl2. Interactions between 1/5DNP38C10 and PmI and NpI units located within the rod section of the dumbbell components of the [2]rotaxane give rise to the appearance of charge-transfer bands, the energies of which correlate with the electron-accepting properties of the two diimide moieties. Comparison between the positions of the visible absorption bands in the three [2]rotaxanes shows that, in NpPmR, the major translational isomer is the one in which 1/5DNP38C10 encircles the NpI unit. Correlations of the reduction potentials for all the compounds studied confirm that, in this non-degenerate [2]rotaxane, one of the translational isomers predominates. Furthermore, after deactivation of the NpI unit by one-electron reduction, the 1/5DNP38C10 macrocycle moves to the PmI unit. Li+ ions have been found to strengthen the interaction between the electron-donating crown ether and the electron-accepting diimide units, particularly the PmI one. Titration experiments show that two Li+ ions are involved in the strengthening of the donor-acceptor interaction. Addition of Li+ ions to NpPmR induces the 1/5DNP38C10 macrocycle to move from the NpI to the PmI unit. The Li+-ion-promoted switching of NpPmR in a 4:1 mixture of CD2Cl2 and CD3COCD3 has also been shown by 1H NMR spectroscopy to involve the mechanical movement of the 1/5DNP38C10 macrocycle from the NpI to the PmI unit, a process that can be reversed by adding an excess of [12]crown-4 to sequester the Li+ ions.     

面向原子制造的框架核酸研究进展

框架核酸是核酸分子通过自组装形成的一维到三维的框架结构,不仅能精准定位功能基元,还可实现在纳米甚至原子级尺度上进行力学、光学和电学等物理性质,以及单分子水平化学与生化反应的精准调控.利用框架核酸对物质进行原子级的人工自组装,可实现基本构筑单元的精准物理排布与功能化集成,进而实现器件制造,有望推动从原子到宏观的精确功能化...     

薄膜生长速率对有机光伏器件性能的影响

采用真空热蒸发镀膜的方法制备了酞菁铜(CuPc)和富勒烯(C60)构成的平面异质结结构光伏器件,并初步研究了CuPc薄膜生长速率对器件光伏性能的影响,我们发现以较大薄膜生长速率制备的器件表现出较大的短路电流和能量转换效率。X射线衍射和原子力显微镜观察的结果表明生长速率较大的CuPc薄膜结晶相含量较少,薄膜结构较均匀、致密、平整,这可能使得CuPc薄膜激子扩散和载流子迁移特性得到提高,也可能改善其与C60受主薄膜和ITO阳极的接触,并有利于载流子的分离和收集,从而表现出较好的光伏特性。     

柔性有机电致发光器件导电基板的工艺性能

在聚对苯二甲酸乙二醇酯(PET)柔性衬底上采用直流磁控溅射技术制备了氧化铟锡(ITO)透明导电薄膜,研究了衬底温度、溅射功率和溅射压强等工艺条件对薄膜光电性能的影响,并利用原子力显微镜(AFM)表征了衬底及ITO薄膜的表面形貌。结果表明,在PET衬底温度50℃、溅射功率100W和溅射压强2.66×10-1Pa的条件下,可以得到低方阻(50Ω/□)和高透过率(>90%)的透明导电薄膜。以此柔性ITO衬底为阳极,制备了结构为PET/ITO/NPB/Alq3/Mg∶Ag的柔性有机电致发光器件,在驱动电压为13V时,器件的发光亮度达到了2834cd/m2。     

基于CAN总线的高分辨率工业显示屏控制器

为了优化工业显示屏,提出一种利用CAN总线的优势来优化工业显示屏控制器的方法。该控制器创新点在于以CAN总线作为传输,控制键和数字输入键的命令集经CAN总线传输到STM32单片机,STM32单片机运算、转换数据后经内部FSMC接口发送给FPGA,FPGA控制数据发送到SDRAM,显示屏由FPGA控制取读SDRAM内部的数据并显示,最大通信距离可达10km,通信速率可达1 Mbit/s。经实验验证,能提高传输速率并且能支持多个设备和高分辨率显示。     

Electrical characterization of poly(amide-imide) for application in organic field effect devices

The admittance spectra and current–voltage (I–V) characteristics are reported of metal–insulator–metal (MIM) and metal–insulator–semiconductor (MIS) capacitors employing cross-linked poly(amide–imide) (c-PAI) as the insulator and poly(3-hexylthiophene) (P3HT) as the active semiconductor. The capacitance of the MIM devices are constant in the frequency range from 10 Hz to 100 kHz, with tan δ values as low as 7 × 10⁻³ over most of the range. Except at the lowest voltages, the I–V characteristics are well-described by the Schottky equation for thermal emission of electrons from the electrodes into the insulator. The admittance spectra of the MIS devices displayed a classic Maxwell–Wagner frequency response from which the transverse bulk hole mobility was estimated to be ∼2 × 10⁻⁵ cm² V⁻¹s⁻¹ or ∼5 × 10⁻⁸ cm² V⁻¹s⁻¹ depending on whether or not the surface of the insulator had been treated with hexamethyldisilazane (HMDS) prior to deposition of the P3HT. From the maximum loss observed in admittance-voltage plots, the interface trap density was estimated to be ∼5 × 10¹⁰ cm⁻² eV⁻¹ or ∼9 × 10¹⁰ cm⁻² eV⁻¹ again depending whether or not the insulator was treated with HMDS. We conclude, therefore, that HMDS plays a useful role in promoting order in the P3HT film as well as reducing the density of interface trap states. Although interposing the P3HT layer between the insulator and the gold electrode degrades the insulating properties of the c-PAI, nevertheless, they remain sufficiently good for use in organic electronic devices.     

反射式液晶器件振幅调制特性的研究

研究了反射式液晶器件(RLCOS)的振幅调制特性.采用2×2的琼斯矩阵计算仿真,从理论上分析了它的振幅调制特性.实验采用He Ne激光为光源,将反射式液晶器件显示器作为液晶空间光调制器,用计算机和相关的电路系统驱动控制,并用CCD采样数据,测试了1024×768反射式液晶器件显示器的振幅调制特性.与未改形光束剖面相比,在特定的入射、出射偏振光配制下,可以用反射式液晶器件显示器来做振幅调制器.     

适用SAW器件的高C轴取向ZnO薄膜制备及性能分析

探讨了高性能ZnO薄膜的制备工艺,利用X射线衍射(XRD)、原子力显微镜(AFM)和高阻仪对各种条件下制备的薄膜进行了表征分析。研究表明:在一定温度范围内随退火温度上升薄膜C轴取向性更优;同时O空位的填充、自由Zn原子的氧化使得薄膜电阻率提高至107Ω·cm数量级;600℃为最佳退火处理温度,600℃退火处理的ZnO薄膜粗糙度小(RMS为2.486nm),且晶粒均匀致密,表面平整,是适于制备声表面波(SAW)器件的高C轴取向、高电阻率及较平坦的ZnO薄膜。