Effect of Bulky Functional Groups on Donor and Acceptor Interactions and their Photoluminescence Properties

Material designs that use donor and acceptor units are often found in organic optoelectronic devices. Molecular level insight into the interactions between donors and acceptors are crucial for understanding how such interactions can modify the optical properties of the organic optoelectronic materials. In this paper, tris(4-(tert-butyl)phenyl)amine (pTPA) was synthesized as a donor in order to compare with unmodified triphenylamine (TPA) in a donor–acceptor system by having 2,4,6-triphenyl-1,3,5-triazine (TRZ) as an acceptor. Dimerization of donors and acceptors occurred in solvent when the concentration of solute is high. At 0 K, using a polarizable continuum model, the nitrogen atom of TPA is found to stack on top of the center of triazine of TRZ, whereas such alignment is offset in pTPA and TRZ. We attributed such alignment in TPA-TRZ as the result of attractive interactions between partial localization of 2p_z electrons at the nitrogen atom of TPA and the π deficiency of triazine in TPA-TRZ. By taking into account random motions of the solvent effect at 300 K in quantum molecular dynamics and classical molecular dynamics simulations to interpret the marked difference in emission spectra between TPA-TRZ and pTPA-TRZ, it was revealed that the attractive interaction between pTPA and TRZ in toluene is weaker than TPA and TRZ. Because of the weaker attractive interaction between pTPA and TRZ in toluene, the dimers adopted numerous ground state conformations resulting in broad emission bands superimposed with multiple small Gaussian peaks. This is in contrast to TPA-TRZ which has only one dominant dimer conformation. This study demonstrates that the strength of intermolecular interactions between donors and acceptors should be taken into consideration in designing supramolecular structures.     

A Photochemical/Thermal Switch Based on 4,4′-Bis(benzimidazolio)stilbene: Synthesis and Supramolecular Properties.

Stilbene derivatives are well-recognised substructures of molecular switches based on photochemically and/or thermally induced (E)/(Z) isomerisation. We combined a stilbene motif with two benzimidazolium arms to prepare new sorts of supramolecular building blocks and examined their binding properties towards cucurbit[n]urils (n=7, 8) and cyclodextrins (β-CD, γ-CD) in water. Based on the ¹H NMR data and molecular dynamics simulations, we found that two distinct complexes with different stoichiometry, i. e., guest@β-CD and guest@β-CD₂, coexist in equilibrium in a water solution of the (Z)-stilbene-based guests. We also demonstrated that the bis(benzimidazolio)stilbene guests can be transformed from the (E) into the (Z) form via UV irradiation and back via thermal treatment in DMSO.     

Core‐Shell Structured Layered Lanthanide‐Organic Complexes with Stilbazolium‐type Dye Encapsulation for Multifunctional Performances

Host‐guest encapsulation of functional organic dye into a porous metal‐organic framework can give rise to the development of new functional materials. In this work, by intercalating the stilbazolium‐type dye (DEAST)I (4′‐diethylamino‐N‐methyl stilbazolium) into four lanthanide layered metal‐organic complexes (Ln‐LMOCs), i. e. {[Ln(BTB)(H₂O)₂]?3(DMF)?2(H₂O)}_n (Ln=La (1), Nd (2), Sm (3), Er (4)), four responsive (DEAST)I@Ln‐LMOC composites have been prepared, serving as multifunctional performance platform. The core–shell structures of (DEAST)I@Ln‐LMOC composites have been fully characterized by IR, UV/Vis, PXRD, SEM, TEM, TGA and ESR. Significantly, after intercalation of dyes, the (DEAST)I@Ln‐LMOC composites exhibit enhanced luminescent sensing properties in detecting Fe³⁺ with much higher water stabilities. The luminescent sensing behavior stems from the fluorescence resonance energy transfer (FRET) from the π‐electron‐rich BTB ligands to the Fe³⁺, and their higher water stabilities are induced by electrostatic interactions and lower porosity. Specially, the characteristic emissions of Sm³⁺ will not be affected after the encapsulation guest dyes, which provide a theoretical guide for the modulation of luminescence devices. Finally, better ion conductivities and diminished photocurrents can be achieved after the embedding of the functional organic dye. In all, the formation of (DEAST)I@Ln‐LMOC composites with core–shell structures can be utilized as a multifunctional platform with good stability.     

MEMS磁场传感器的设计及测试

以U型梁为主要结构设计了一种新型的洛伦兹力驱动的磁场传感器,检测在磁场中作切割磁力线运动的金属线上的感生电压,实现磁场测量.首先介绍了传感器的工作原理,并用振动理论对传感器的受力及响应进行了分析,接着用有限元软件建立结构模型并对其振动模态和频率进行了仿真.该MEMS磁场传感器采用标准的CMOS工艺加上后处理来实现.最后...     

热连轧活套系统的分散控制

分析热连轧轧制速度增量对活套系统性能的影响,建立了活套关联系统模型,提高了活套系统模型精度.基于H∞原理,将活套高度与张力系统之间的耦合影响看作扰动,采用分散控制方式,为每台轧机活套系统单独设计控制器.仿真结果表明,基于活套关联系统模型,采用分散方式设计控制器,提高了活套系统的控制性能.     

有界变参数车道保持准滑模控制

假定车辆质量、转动惯量、轮胎侧偏刚度等参数具有不确定性,考虑时变有界和慢变未知两种情况,研究了自动化公路系统车道保持控制方法.基于位置预瞄策略和车辆横向动力学模型,建立预瞄点处的车辆横向位置误差和横摆角误差动态方程;采用准滑模控制方法,设计车道保持变结构控制规律;基于李雅普诺夫稳定性理论,对控制系统的稳定性进行分析.仿真实验表明,采用文中设计的控制方法,在达到满意跟踪性能的同时,还能有效抑制颤振,对参数不确定性具有鲁棒性.     

采用BP神经网络的基波高精度检测方法

提出一种基于BP(Back Propagation)神经网络的电网基波频率和幅值的高精度检测方法。正弦信号过零点两侧对称两点连线与时间轴的交点和频率满足单调关系,但并非严格的线性关系,而且与幅值无关,据此用BP神经网络建立该交点与频率的映射关系,并提出了对称点优化选取方法。仿真表明,提出的算法对频率的检测精度达到10-4,幅值的检测精度高达10-5,远远高于普通傅里叶变换(Fast Fourier Transfromation, FFT)算法和FFT加Hanning窗算法;随机噪声和谐波对该方法测量精度的影响很小,具有较强的抗干扰能力。     

采煤机自适应记忆切割

针对以往的采煤机记忆切割技术在我国复杂地质条件下不适用的情况,提出了基于模糊控制理论的采煤机自适应记忆切割技术,设计出了采煤机位置、姿态定位系统和采煤机自适应切割模糊控制系统.该系统可以获取采煤机任意位置处的姿态和状态信息,自动跟踪所记忆的切割路径,基于模糊控制理论对是否截割到岩石进行判断并做出最优的处理方案.通过实验室的路径跟踪实验和西安煤矿机械有限公司的自适应调节实验证明:该技术在实现采煤机记忆切割的基础上能够识别出滚筒到切割岩石时的异常状态,并对牵引速度和滚筒高度做自适应调节,能够满足复杂地质条件下对采煤机的控制要求.     

用渐近变分法对复合材料层合板简化数值建模及仿真

为有效分析三维复合材料层合板非线性、单向耦合弹性问题,基于渐近变分方法构建单斜对称的复合材料层合板的简化模型。推导了基于旋转张量分解概念的复合材料层合板能量表达式;利用渐近变分法将三维层合板严格拆分为二维板分析和沿法线方向的一维非线性分析;进行了降维后近似能量推导及reissner形式转换;提供了三维场重构关系以得到沿厚度方向的准确应力分布。通过对一具有四层复合层合板的柱形弯曲算例表明:基于该理论和重构过程开发的渐近变分程序VAPAS重构生成的三维应力场精确性较古典层合理论更好,与三维有限元精确解相一致。     

Banach空间中有限族“三解合一”的混合临近点法

在一致凸一致光滑的Banach空间中引进了一个新的混合迭代序列,利用混合临近点法,找到了均衡问题与变分不等式及有限族半相对非扩张映射不动点问题的公共解(简称"三解合一"),并证明了该迭代序列强收敛到其公共解.所得结果改进和推广了已有的相应结果.