KINETICS AND MECHANISM OF THE REACTION BETWEEN OLIGOSILOXANES AND P-TRICHLORO-N-DICHLOROPHOSPHORYL MONOPHOSPHAZENE (Cl3P[dbnd]N-POCl2)

Abstract

³¹P NMR investigation has been made of the action of Cl₃P[dbnd]N-POCl₂(I) first on hexamethyldisiloxane (Me₃Si)₂O and then on oligosiloxanes Me₃Si-(OSiMe₂)_n-OSiMe₃ n = 2 and n=3. The reactions were carried out in bulk or in solution with molar ratios siloxane/(I) varying from I to 5. It was demonstrated that only the monosubstitution of a chlorine atom by the -(OSiMe₂)_n,-OSiMe₃ species n = 0, 2, 3 with elimination of trimethylchlorosilane occurred leading to the derivatives Cl₂OP-N[dbnd]PCl₂O(SiMe₂-O)_nSiMe₃ (II). For n=2, 3 the siloxane redistribution reactions were observed by ²⁹Si NMR analysis. A two steps mechanism is proposed. consisting in a nucleophilic substitution, involving a tricoordinate phosphazenium intermediate, followed by the formation of an active ionic centre probably an oxonium ion, arising from the solvatation by the siloxane of this phosphazeniurn ion and /or of (II) leading to the redistribution reactions. The influences of the solvent, of trimethylchlorosilane, of the temperature, and of the addition of a protonated species (MDH) were investigated.     

Factors affecting the strengths of σ-hole electrostatic potentials

A σ-hole is a region of diminished electronic density on the extension of a covalent bond to an atom. This region often exhibits a positive electrostatic potential, which allows attractive noncovalent interactions with negative sites. In this study, we have systematically examined the dependence of σ-hole potentials upon (a) the atom having the σ-hole, and (b) the remainder of the molecule. We demonstrate that not only relative electron-attracting powers need to be considered, but also relative charge capacities (or polarizabilities), and that other factors can also have significant roles.     

Effect of epitaxial crystallization on packet-like space charge characteristics in low-density polyethylene under multi-field coupling conditions

In order to study the effect of epitaxial crystallization on charge transport in low-density polyethylene (LDPE) under multi-field coupling conditions, three typical epitaxial crystallizations, namely disorder (glass substrate), crossover (isotactic polypropylene substrate), and parallel (polytetrafluoroethylene substrate), were prepared and denoted as LD-G, LD-iPP, and LD-PT, respectively. Packet-like space charge through samples was analyzed by the pulsed electro-acoustic (PEA) method. It is shown that different microscopic surface morphologies appeared in the LDPE samples with different epitaxial crystallizations, which, however, do not change the crystalline structure of the bulk. Packet-like space charge phenomena were observed and the distortion field increased with the temperature which could be attributed to the larger amount of charge injection in a shorter period. The differences of the amount and injection rate of the space charge were explained and verified considering the typical chain alignment of epitaxial crystallization, which, in our opinions, contributes to the pass over of positive charge in LD-iPP samples.     

Dielectric barrier discharge in needle-to-plane configuration: Model of surface charge relaxation

Relaxation process of surface charge owing to dielectric barrier discharge (DBD) in “needle – air gap – polyethylene terephthalate film – plane” configuration is considered. Experimental data of the surface charge relaxation (SCR) are obtained by means of the rotating capacitive probe. Taking into account Gaussian radial distribution of accumulated charge density, effective surface and volume electrical conductivities of a barrier dielectric, phenomenological model of SCR for any dielectric thickness is proposed and exact solutions are obtained. The adequacy of the model is confirmed by the numerical computation. There is a good agreement between the experimental results and the model calculations.     

Improvement charge injection in P-type polymer field-effect transistors with low-cost molybdenum electrodes through dodecanoic acid self assembled monolayer

Most of the merit of organic thin film transistors (OTFTs) is that they can be manufactured using cost effective processes. However, expensive gold (Au) electrodes have usually been used as a source/drain (S/D), due to their benign energy level matching, high air stability, and easy patternability. In this article, we report a simple method for improving the charge injection from a low cost molybdenum (Mo) electrode to organic semiconductors in OTFTs by incorporating a dodecanoic acid (DA)–based self-assembled monolayer (SAM). The OTFT performance is remarkably improved when compared to the devices with a pristine Au electrode. The hole carrier mobilities (hole μ_FET) were ～0.13 (rr-P3HT), ～0.55 (PC12TV12T) and ～0.72 (P2100) cm²/V·sec.     

Macrocycles consisting of flexible and rigid segments: enforced folding and host-guest inclusion exciplex formation

Macrocycles consisting of two tris(phenylene ethynylene) (or tri-PE) units connected via two flexible linkers adopt an ‘unfolded’ conformation that is converted into a folded conformation upon introducing intramolecular hydrogen bonding interaction. These foldable macrocycles are capable of forming inclusion charge transfer (CT) complex with electron-deficient small aromatics.     

Optical manipulation of charged microparticles in polar fluids

In this study, we report a systematic study of the response of a charged microparticle confined in an optical trap and driven by electric fields. The particle is embedded in a polar fluid, hence, the role of ions and counterions forming a double layer around the electrodes and the particle surface itself has been taken into account. We analyze two different cases: (i) electrodes energized by a step‐wise voltage (DC mode) and (ii) electrodes driven by a sinusoidal voltage (AC mode). The experimental outcomes are analyzed in terms of a model that combines the electric response of the electrolytic cell and the motion of the trapped particle. In particular, for the DC mode we analyze the transient particle motion and correlate it with the electric current flowing in the cell. For the AC mode, the stochastic and deterministic motion of the trapped particle is analyzed either in the frequency domain (power spectral density, PSD) or in the time domain (autocorrelation function). Moreover, we will show how these different approaches (DC and AC modes) allow us, assuming predictable the applied electric field (here generated by plane parallel electrodes), to provide accurate estimation (3%) of the net charge carried by the microparticle. Vice versa, we also demonstrate how, once predetermined the charge, the trapped particle acts as a sensitive probe to reveal locally electric fields generated by arbitrary electrode geometries (in this work, wire‐tip geometry).     

N3/Al2O3/N749交替组装结构拓宽准固态染料敏化太阳能电池光响应范围和界面修饰效果

研究了染料敏化太阳能电池(DSCs)中N3/Al₂O₃/N749交替组装结构的作用. 该结构使用Al₂O₃作为介质层吸附第二层染料, 可以有效拓宽DSCs的光响应范围, 提高电池的光电转化效率. UV-Vis 吸收光谱和单色光转换效率(IPCE)谱测试结果表明, 相对于单一染料, 使用交替组装结构的电池光响应范围变宽. 电流-电压(I-V)曲线结果表明, 该结构有效增加了DSCs 电池的光电转化效率, 从单一N3 和N749 染料的4.22%和3.09%增加到了5.75%, 分别增加了36%和86%. 为了研究该结构的作用机理, 本文对其界面修饰作用及界面电子过程进行了讨论. 暗电流测试结果表明交替组装结构可以有效阻止电荷复合过程; 电化学阻抗谱(EIS)结果表明在黑暗条件下, N3/Al₂O₃/N749结构可以提高界面电阻, 从而抑制电荷复合过程; 本文建立了等效电路模型, 并使用该模型讨论了交替组装结构的界面电子过程; 调制强度光电流谱(IMPS)和调制强度光电压谱(IMVS)的结果表明该结构可以提高电子寿命和改善电子扩散.     

Rational design of donor–π–acceptor n-butyl-1,8-naphthalimide-cored branched molecules as charge transport and luminescent materials for organic light-emitting diodes

Four D–π–A bipolar molecules with n-butyl-1,8-naphthalimide (BNI) fragments as acceptors, acetylenes as π-spacers, and different aromatic groups as donors have been designed to explore their optical, electronic, and charge transport properties as charge transport and luminescent materials for organic light-emitting diodes (OLEDs). The frontier molecular orbitals (FMOs) and local density of states analysis have turned out that the vertical electronic transitions of absorption and emission are characterized as intramolecular charge transfer (ICT). The calculated results show that their optical and electronic properties are affected by the different donors of the bipolar molecules. Our results suggest that D–π–A 1,8-naphthalimide derivatives with donors triphenylamine (1), 1-nitrobenzene (2), anisole (3), and 4-phenylbenzo[c][1,2,5]thiadiazole (4) fragments are expected to be promising luminescent materials. Furthermore, 2–4 are expected to be promising candidates for both electron and hole transport materials as well as potential ambipolar charge transport material, whereas BNI and 1 can serve as hole transfer materials only. We have also predicted the mobility of 4 with better performance in three different space groups. On the basis of investigated results, we proposed a rational way for the design of charge transport and/or luminescent materials simultaneously.