二次配体结构和[CuCl4]2－构型对层间隧道结构的影响研究

设计合成的质子配体, N,N,N’,N’-四(对甲基苄基)乙二胺(SL1)和N,N,N’,N’-四苄基乙二胺(SL2), 是连有大体积取代基团的含N双齿配体, 它可通过二次球形配位, 与第一络合物[CuCl4]2－形成层间隧道框架结构. 环戊醇分子和乙醇分子分别被填入由SL1和SL2构筑的隧道中, 形成包结化合物. 晶体结构分析结果表明, 这样的配体易于与指导基团通过NH＋…Cl－氢键作用进行双齿配位并形成1D带和2D层结构; SL1 2D层间的苄基呈平行堆砌, 形成1D亲水性隧道框架, SL2 2D层间的苄基呈交错堆砌, 形成了1D疏水性隧道框架. 实验结果表明, 层间隧道框架结构的孔径及极性与第二配体的分子长度、指导基团的构型以及客体分子的形状大小有关.     

D-π-A-π-D型萘基衍生物的电子、光谱和电荷传输性质

采用量子化学方法研究了给体-π桥-受体-π桥-给体(D-π-A-π-D)型萘基衍生物及其“CH”/N 杂原子取代衍生物的电子、光谱和电荷传输性质. 计算结果表明, 分子结构的变化引起了电子结构和能隙的变化, 进而改变了吸收和发射光谱. 其中, 衍生物的最大发射波长几乎覆盖了可见光区域(447.7-743.1 nm). 而且, 光谱的Stokes 位移较大(106.1-222.4 nm), 产生的原因在于, 与基态结构相比较, 衍生物的激发态结构中分子主干存在两个相连部分更为平面的构型. 计算结果还显示, 所有衍生物都可以作为有机电致发光二极管中的空穴传输材料.     

选择性合成手性八氢NOBIN和四氢NOBIN

通过部分氢化手性的(S)-NOBIN [(S)-2-氨基-2’-羟基-1,1’-联萘]选择性地合成了(S)-H8-NOBIN和(S)- -NOBIN. 弱极性溶剂(环己烷)和强极性溶剂(2,2,2-三氟乙醇和含乙酸的乙醇)几乎专一地得到(S)-H8-NOBIN (92%). 而中等极性溶剂(甲醇, 乙醇和异丙醇)以中等产率得到(S)- -NOBIN (66%).     

利用salen型荧光探针测定Cr3+

研究了salen型席夫结构的荧光探针N,N’-二(2-羟基-1-萘甲醛)-l,2-苯二胺(NAPPDIH)对Cr3+的响应。Cr3+能够使该探针的荧光猝灭。研究表明,在pH3.5(乙酸胺-盐酸)和DMSO/H2O(V/V,8:2)的条件下,8.0×10-6 mol/L的Cr3+可以导致NAPPDIH 65%的荧光猝灭。并且,Cr3+的浓度在5.0×10-7～8.0×10-6 mol/L的范围内,与荧光强度的变化值呈良好的线性关系,检出限为3.7×10-7 mol/L。方法可用于直接检测水样中的Cr3+。     

HATU介导的苯硼酸快速接枝羟丙基壳聚糖反应

苯硼酸(PBA)在水溶液中可与顺-1,2-二醇或1,3-二醇形成可逆共价键,常在纳米/水凝胶中用作葡萄糖响应单元或动态交联基团.本文提供了一种快速合成苯硼酸接枝壳聚糖衍生物(CPBA-HPCS)的方法.以羟丙基壳聚糖(HPCS)为原料, 2-(7-偶氮苯并三氮唑)-N,N,N’,N’-四甲基脲六氟磷酸酯(HATU)为缩合剂,在二甲基亚砜(DMSO)中反应1 h即可得到在pH>8.5的水溶液中可溶的CPBA-HPCS.采用傅里叶变换红外光谱(FTIR)和核磁共振波谱(NMR)对该衍生物结构进行验证,并对反应动力学进行了研究,得到了一系列不同取代度的CPBAHPCS,其取代度最高可达0.78.这种新的壳聚糖衍生物在制备智能水凝胶和药物载体方面具有较好的应用前景.     

N’,N’-二乙基硫脲添加剂对铜微沉积工艺电化学行为的影响

为了研究N’,N’-二乙基硫脲添加剂在微沉积工艺中对铜金属孔洞填充能力的影响, 采用线性伏安法(LSV)、循环伏安法(CV)、SEM测量法分析比较了无添加剂、含硫脲和含N’,N’-二乙基硫脲添加剂时微沉积铜工艺中的电化学行为, 并借助塔菲尔方程, 分析比较此三种情况下电镀反应过程中的电极动力学参数. 结果显示: 当铜微沉积工艺中加入N’,N’ -二乙基硫脲添加剂时, 产生活性极化, 该活性极化效应降低铜离子的放电速度, 抑制孔洞边缘部分沉积较快区域的过快生长; 同时活性极化提高, 将导致成核点的增加, 沉积膜的晶粒较小, 镀膜也较平滑细致, 实验测得铜离子的平滑能力比没有添加剂时提高约50%. 最后通过微沉积工艺成功地将金属铜填充入宽为10 μm, 深宽比为4∶1的微型凹槽中, 且镀层内没有空洞、空隙以及细缝等缺陷.     

新型萘酰亚胺衍生物的合成

N-(N’,N’-二甲基氨基乙基)-4-硝基-1,8-萘酰亚胺和2,3-二甲基苯并噻唑碘化盐在痕量水存在下经亲核取代反应合成了一个新型的萘酰亚胺衍生物——N-(N’,N’-二甲基氨基乙基)-4-[2-(2,3-二氢-2,3-二甲基苯并噻唑)氧基]-1,8-萘酰亚胺,其结构经1H NMR,13C NMR和ESI-MS表征。并对反应机理进行了初步研究。     

基于三萘苯的溶液可加工螺旋形寡聚物的合成及其在蓝光有机电致发光器件中的应用

近年来,人们在有机电致发光材料和器件结构方面取得了巨大的进步。然而由于蓝光材料具带隙宽的内禀属性,在发光效率、色纯度和稳定性上仍然面临巨大挑战。本文将螺旋形三萘苯共轭体系引入电致发光材料领域,它独特的螺旋形分子结构和易于化学修饰的特点有利于抑制聚集体和基激缔合物的形成。通过SiCl₄催化的环三缩合反应和Suzuki偶联反应,我们设计合成了以三萘基苯为核心,萘、蒽和三苯胺为取代基团的系列螺旋形蓝光寡聚物,并系统地研究了它们的热学、光物理和电化学性质。研究发现,萘和三苯胺取代的寡聚物1, 3, 5-三(3-(1-甲氧基萘-2-基)-4-甲氧基萘-1-基)苯(TNNB)和1, 3, 5-三(3-(4-(N, N-二苯胺基)苯基)-4-甲氧基萘-1-基)苯(TPANB)具有最好的热稳定性。在溶液中,这两种材料都具有深蓝发射,发射峰分别为382和415 nm;在薄膜中, TNNB的发射峰仅有1 nm的红移,而TPANB甚至产生了6 nm的蓝移。以这些寡聚物为发光材料,通过旋涂法制备的有机电致发光器件结果表明,基于TNNB的器件获得了最大亮度达到5273 cd·m^-2,色坐标(0.17, 0.11)的纯蓝光器件。     

基于9,9'-螺二芴和萘的纯碳氢主体材料（英文）

利用磷光有机发光二极管的主客体掺杂结构有助于避免三重态激子浓度猝灭,从而提高器件性能.9,9’-螺二芴(SBF)及其衍生物具有独特的正交构型和刚性骨架,具有高玻璃化转变温度、高三线态能级和用作主体材料的潜力.通过引入萘环合成并表征了两种基于SBF的纯碳氢化合物(PHC)磷光发光器件的主体材料,命名为1,4-SBF-Nap和1,8-Oct-Nap.其中,1,8-Oct-Nap分子存在一个有趣的环化反应,形成八原子环结构而不是一般的SBF.以Ir(MDQ)₂(acac)为客体,成功制备了基于这两种主体的红光器件,最大外量子效率(EQE)分别为15.0%和13.7%,证明PHC主体材料在设计上的多样性.     

双希夫碱-N,N’-二(2-羟基-1-萘甲醛)缩-1,4-苯二胺的电子光谱和光致变色机理研究

测定了双希夫碱,N,N＇-二(2-羟基-1-萘甲醛)缩-1,4-苯二胺(BNP)在环己烷和乙腈中的稳态和瞬态吸收光谱以及稳态荧光光谱,讨论了光致变色机理.在非极性溶剂中,BNP以烯醇式为主要存在形式,最大吸收位于紫外区.在极性溶剂中,既有烯醇式,又有质子转移产物的吸收,但以前者为主.无论在极性还是非极性溶剂中,其荧光发射都是来源于质子转移产物的激发态.     

Synthesis and Crystal Structure of 4,4′-Diamino-N,N′-diethyl Bisbenzenesulfamide

A new compound of 4,4′-diamino-N,N′-diethyl bisbenzenesulfamide (C18H26N4O4S2, Fw = 426.55) has been synthesized and its structure was determined by X-ray crystallography method. The crystal belongs to the monoclinic system, space group P21/c with a = 10.0623(9), b = 13.6759(13), c =15.5309(14) , β = 100.482(2)o, V = 2101.6(3) 3, Dc = 1.348 g/cm3, F(000) = 904, μ = 0.285 mm–1, Z = 4, the final R = 0.0512 and wR = 0.1363 for 3485 observed reflections with I > 2σ(I). The structure of the title compound is pseudo secondary axisymmetric, and the two sulfamide-groups show distorted tetrahedral configurations.     

含三苯胺的二苯乙烯化合物的合成及其电致发光性能

电致发光器件在光通讯、光信息处理、视频器件、测控仪器等光电子领域有着广泛而重要的应用价值.无机半导体二极管、半导体粉末、半导体薄膜等电致发光器件尽管已取得了令人注目的成就,但由于其复杂的器件制备工艺,高驱动电压、低发光效率,不能大面积平板显示,能耗较高以及难以解决短波长(如蓝光)等问题,使得无机电致发光材料的进一步发展受到一定的影响.     

17.1%-Efficiency organic photovoltaic cell enabled with two higher-LUMO-level acceptor guests as the quaternary strategy

Quaternary blended organic solar cells utilize four blended material components(one donor plus three acceptors, two donors and two acceptors, or three donors plus one acceptor) as the active layer materials. The use of four material components allows us to have more material selections and more mechanism choices to improve the photon-to-electron conversion efficiency. In this contribution, we present a new case of quaternary material system, that shows 17.1% efficiency obtained by adding IDIC and PC_(71)BM as the guest acceptors of the host binary of PM6:Y6. The lowest unoccupied molecular orbital(LUMO) levels of IDIC and PC_(71)BM are both higher than that of Y6, which is one reason to obtain increased open-circuit voltage(V_(oc)) in the quaternary device. Upon introduction of IDIC and PC_(71)BM as the acceptor guests, the hole and electron mobilities are both increased, which contributes to the increased short-circuit current-density(J_(sc)). Effects of the weight ratios of the three acceptor components are investigated, which demonstrates that the increased hole and electron mobilities, the accelerated hole-transfer, and the reduced monomolecular recombination are the factors contributing to the increased J_(sc)and fill-factor. This case of quaternary device demonstrates the applicability of the quaternary strategy in increasing the device functions and hence the efficiencies in the field of organic photovoltaic cells.     

三重态发光材料Cu4掺杂的PVK发光器件及特殊的发光增强机理研究

多种有机发光材料已被应用于电致发光（EL）器件的制备，其荧光效率远比无机发光材料高。与光激发直接产生单重态洋鬼子不同，电致发光过程是电子空穴分别由相反极性的电极注入（非成对电子注入），三重态和单重态激子同时生成，按自旋统计理论预测，三重态和单重态子的比例为3：1。由于三重态的跃迁是自旋禁阻的，大部分有机分子的三重态激子发光效率极低，有机电致发光器件的最高交率限制在25％（对于光致发光效率100％的理想情况）。为进一步提高器件效率，人们开始设想和实施对通常认为是无效激发的75％的三重激发态进行利用，其关键是筛选出适于器件应用的高效率三重态发光材料，据此我们选择过渡金属配合物Cu4(C≡CPh4)4L2[L=1,8-bis9diphenyl phosphino)-3,6-dioxaoctane]（以下简称Cu4）进行了器件性能研究。     

以N,N-四(间联苯基)-4,4-联苯二胺为正孔传送材料的有机电致发光器件(英文)

用新的路径成功地合成了N,N -四(间联苯基)-4,4 -联苯二胺(m TBPBz).以m TBPBz作为正孔传送材料,探讨了它在有机电致发光器件中的应用.制作了结构为玻璃基板／ITO阳极(130nm)／m TBPBz(40nm)／Alq(60nm)／LiF(0.5nm)／Al阴极(100nm)的器件.结果显示:该有机电致发光器件的绿色发光来源于Alq层.10V时,它的最大亮度为9486cd／m2.证明了m TBPBz具有正孔传送性能,可作为电致发光材料使用.     

Experimental and theoretical study of three new benzothiazole-fused carbazole derivatives

Three new D-π-A type compounds, each containing one benzothiazole ring as an electron acceptor and one N-ethylcarbazole group as electron donor, were synthesized and characterized by elemental analysis, NMR, MS and thermogravimetric analysis. The absorption and emission spectra of three compounds were experimentally determined in several solvents and were simultaneously computed using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The calculated reorganization energy for hole and electron indicates that three compounds are in favor of hole transport than electron transport. The calculated absorption and emission wavelengths are well coincident with the measured data. The calculated lowest-lying absorption spectra can be mainly attributed to intramolecular charge transfer (ICT). And the calculated fluorescence spectra can be mainly described as originating from an excited state with intramolecular charge transfer (ICT) character. The results show that three compounds exhibited excellent thermal stability and high fluorescence quantum yields, indicating their potential applications as excellent optoelectronic material in optical field.     

Two-dimensional MgSiP_2 with anisotropic electronic properties and good performances for Na-ion batteries

Using the global particle-swarm optimization method and density functional theory,we predict a new stable two-dimensional layered material:MgSiP_2 with a low-buckled honeycomb lattice.Our HSE06 calculation shows that MgSiP_2 is an indirect-gap semiconductor with a band-gap of 1.20 eV,closed to that of bulk silicon.More remarkably,MgSiP2 exhibits worthwhile anisotropy along with electron and hole carrier mobility.A ultrahigh electron mobility is even up to 1.29 × 104 cm~2 V ~1 s ~1.while the hole mobility is nearly zero along the a direction.The large difference of the mobility between electron and hole together with the suitable band-gap suggest that MgSiP_2 may be a good candidate for solar cell or photochemical catalysis material.Furthermore,we explore MgSiP2 as an anode for sodium-ion batte ries.Upon Na adsorption,the semiconducting MgSiP2 transforms to a metallic state,ensuring good electrical conductivity.A maximum theoretical capacity of 1406 mAh/g,a small volume change(within 9.5%),a small diffusion barrier(～0.16 eV) and low average open-circuit voltages(～0.15 V) were found fo r MgSiP2 as an anode for sodium-ion batteries.These results are helpful to deepen the understanding of MgSiP2 as a nanoelectronic device and a potential anode for Na-ion batteries.     

Aerogen Bonding Interaction: A New Supramolecular Force?

We report evidence of the favorable noncovalent interaction between a covalently bonded atom of Group 18 (known as noble gases or aerogens) and a negative site, for example, a lone pair of a Lewis base or an anion. It involves a region of positive electrostatic potential (σ‐hole), therefore it is a totally new and unexplored σ‐hole‐based interaction, namely aerogen bonding. We demonstrate for the first time the existence of σ‐hole regions in aerogen derivatives by means of high‐level ab initio calculations. In addition, several crystal structures retrieved from the Cambridge Structural Database (CSD) give reliability to the calculations. Energetically, aerogen bonds are comparable to hydrogen bonds and other σ‐hole‐based interactions but less directional. They are expected to be important in xenon chemistry.     

Benzodicarbomethoxytetrathiafulvalene derivatives as soluble organic semiconductors

A series of new tetrathiafulvalene (TTF) derivatives bearing dimethoxycarbonyl and phenyl or phthalimidyl groups fused to the TTF core (6 and 15-18) has been synthesized as potential soluble semiconductor materials for organic field-effect transistors (OFETs). The electron-withdrawing substituents lower the energy of the HOMO and LUMO levels and increase the solubility and stability of the semiconducting material. Crystal structures of all new TTF derivatives are also described, and theoretical DFT calculations were carried out to study the potential of the crystals to be used in OFET. In the experimental study, the best performing device exhibited a hole mobility up to 7.5 × 10(-3) cm(2) V(-1) s(-1)).     

具有高分子空穴传输性能的含三芳胺侧链接枝聚苯乙烯的合成与表征

三芳胺类聚合物作为空穴传输材料具有广泛的应用前景。设计、合成了一种新的三芳胺衍生物单体 4 -乙烯基苄氧基亚甲基三苯胺 ,通过NMR、IR及MS等手段对其结构进行了表征。用AIBN引发新单体进行自由基聚合反应 ,得到了侧链带三苯胺基团的高分子空穴传输聚合物 ,该聚合物具有较高玻璃化转变温度及高热稳定性。