有机金属聚合物/多酸纳米杂化LB膜的制备与光电性质研究

以含有共轭大π键的有机金属聚合物(OMP)作有机组分, 以Keggin结构和Dawson结构钨(钼)磷杂多酸作无机组分, 以十八胺为辅助成膜剂, 用LB技术制备了3种新型有机金属聚合物/十八铵/杂多阴离子OMP/ODA/HPA (HPA＝PMo₁₂, PW₁₂, P₂Mo₁₈)杂化LB膜. 用π-A曲线﹑UV-vis吸收光谱﹑荧光光谱﹑原子力显微镜(AFM)﹑扫描隧道显微镜(STM)和表面光电压谱(SPS)对标题LB膜的成膜性能及光电性质进行了研究, 结果表明标题杂化LB膜的崩溃压为26.8 mN/m, 在可见光区有较强的光电压响应, 并有好的发光性质. 当电压为±8.0 V时, 隧道电流是－0.1～－2.3 nA.     

2,5-双(乙炔基二茂铁)噻吩/钨磷杂多酸纳米杂化LB膜的制备与光电性质研究

以含有共轭大π键的2,5-双(乙炔基二茂铁)噻吩(BFET)和二甲基双十八烷基铵(DMDOA)与Keggin结构和Dawson结构钨磷杂多酸做成膜材料, 用LB技术组装了两种新型无机-有机杂化LB膜. 用π-A曲线、UV-vis吸收光谱、原子力显微镜(AFM)、扫描隧道显微镜(STM)、荧光光谱和表面光电压谱(SPS)对标题LB膜的成膜性能、结构及光电性质进行了研究, 发现标题杂化LB膜的粒子具有纳米尺寸, 在可见光区有较强的光电压响应, 在电压为±2.0 V时, 隧道电流值达到±100 nA.     

8-羟基喹啉两亲配合物的LB膜及其电致发光器件研究

制备了两亲配体N-十六烷基-8-羟基-2-喹啉甲酰胺(HL)十个配合物的LB膜。采用π-A等温线和小角X射线衍射等方法研究了这些LB膜的性质和结构。两亲配合物的单分子占有面积为(1.25±0.06)nm^2和(0.75±0.06)nm^2,分别对应于两亲分子中两个喹啉环平躺和环与环之间以一定的角度倾斜于气/水界面。LB膜内分子排列是二维有序的超晶格结构,双层高度(5.0±0.1)nm;LB膜具有导电各向异性,其平面和垂直直流电导率分别为10^-^5S.m^-^1和10^-^9S.m^-^1;LB膜的高荧光性质使之可以用作为电致发光器件的发光材料。以LaL~2(H~2O)~4Cl的LB膜为发光层的单层电致发光器件的驱动电压为9V,发光亮度330cd/m^2,为黄绿色发光。     

聚N-[5-(8-羟基喹啉)甲基]苯胺/介孔五氧化二钒杂化材料的制备与表征

采用原位插层聚合法制备出层状有序的聚N-[5-(8-羟基喹啉)甲基]苯胺/介孔五氧化二钒(PNQA/Meso-V2O5)杂化材料.结果显示,PNQA插入后,Meso-V2O5的层间距由2.4nm增加到2.81nm,得到的杂化材料仍保持良好的层状结构.杂化材料的室温电导率比Meso-V2O5高出3个数量级.荧光分析表明,在乙醇介质中杂化材料的发射谱带与PNQA相比蓝移22nm,杂化材料的荧光量子产率(26%)明显高于PNQA(10%).     

多金属氧簇与倍半硅氧烷簇构筑的哑铃形杂化分子Langmuir膜和Langmuir-Blodgett膜

以两个形状杂化分子(Shape Hybrid Molecules)为目标分子, 研究了它们在气液界面上形成Langmuir膜的过程和Langmuir-Blodgett (LB)膜的聚集态结构. 杂化分子是由Wells-Dawson型磷钨氧簇(Polyoxometalates, POMs)和T₈型的倍半硅氧烷簇(Polyhedral Oligosilsesquioxane, POSS), 通过对苯二甲酸有机连接链(OL)用共价键构筑的具有杂化性质和哑铃形状的簇-簇杂化分子(POM-OL-POSS). 这两种杂化分子的差别在于POSS段中, 外围有机基团的尺寸不同. 在实验中, 采用Langmuir和LB膜技术, 了解POSS外围的七个取代基变化导致的分子尺寸变化对Langmuir膜形成过程和LB膜结构的影响. 采用Langmuir技术测定了表面压-平均分子面积(π-A)等温曲线和π-A循环等温曲线, 跟踪并研究了这两个杂化分子在水表面上形成Langmuir膜的过程. 实验结果表明, 两个杂化分子都表现出良好的两亲性, 从气相变化到固相的过程中, 杂化分子经历了从分散到集中的过程. 将这些膜转移到基片上, 得到单层的LB膜, 再利用原子力显微镜(AFM)和透射电子显微镜(TEM)研究了LB膜的表面形貌和聚集态结构. 由于POM段中含有钨和钒金属, 可以直接用TEM观察聚集态结构, 发现了在气-液和液-固相转变过程中, LB膜中杂化分子的聚集态结构都呈现涨落特征, 一种凝聚态物理中由相转变导致结构涨落的重要物理现象. 本研究获得的结果能够帮助我们以及这个领域的研究者们继续优化杂化分子的结构, 进一步构筑具有有序结构的膜和本体材料.     

2-(1-萘基偶氮)-咪唑的合成及组装Langmuir-Blodgett膜

合成了一个非典型两亲性分子,2-(1-萘基偶氮)-咪唑(2-NDIM),对它在气/液界面上的组装和LB膜性质进行了研究。结果表明:2-NDIM不能在水相表面形成Langmuir膜,在Ag NO3水溶液亚相中能形成稳定、均匀的配位聚合物单分子膜,组装的LB膜为J-聚集体,最大吸收波长为403nm,归属于反式-N=N-双键的π-π*电子跃迁,光激发LB膜中偶氮基团的反-顺异构化作用不明显,具有较低的反-顺光异构化量子产率。     

酞菁铜化合物LB膜的制备及结构形态研究

利用LB技术研究了带有4个长碳氢链的酞菁铜化合物(CuC12Pc)的单分子膜及它与十八胺(ODA)、二十酸(AA)的混合LB膜的聚集结构形态. 结果表明这种酞菁铜化合物在气液界面上可以形成比较稳定有序的双层Langmuir膜, 且可以转移质量较好的多层LB膜. 利用原子力显微镜(AFM)研究了酞菁铜分子的聚集体结构, 发现CuC12Pc/AA混合膜表现为网状的聚集结构, 而CuC12Pc/ODA混合膜形成长岛颗粒状聚集, 并结合UV-Vis吸收光谱讨论了酞菁铜分子形成不同聚集结构的原因.     

聚乙烯咔唑/杂多阴离子杂化LB膜的制备、结构与光电性质

首次选用聚乙烯咔唑（PVK）、二十二烷酸（BA）与杂多阴离子用LB技术制备 了五种有机/无机杂化LB膜，PVK/BA/HPC（HPC = Na_5(PZ(H_2O)Mo_(11)O_(39)]· 5H_2O, Z = Mn, Co, Cu, Zn, Ni）。用原子力显微镜（AFM），UV-vis，小角X射 线衍射（LAXRD），表面光电压谱（SPS），荧光光谱等对LB膜的结构与性质进行了 表征。结果表明：它们在空气/水界面有好的成膜性能，崩溃压为22 ～27 mN/m， 杂多阴离子作为一个单层夹在PVK和BA双层之间。PVK/BA/HPC LB膜的光致发光具有 PVK激基缔合物的特征荧光，其光电压谱有较强的光电响应。     

金属氯化物-苯并噻唑有机-无机杂化化合物的合成、表征及荧光性质（英文）

金属卤化物MCl2(M=Pb~(2+),Cd~(2+),Co~(2+))分别与苯并噻唑(btz)在浓盐酸中、80℃下反应,合成了3种有机-无机杂化化合物:(btzH)[(PbCl_3)](1),(btzH)_2[CdCl_4]·2H_2O(2)和(btzH)2[CoCl_4]·2H_2O(3),其中化合物2和3结构相似。对化合物1~3进行了粉末衍射、红外和紫外光谱、元素分析、热重分析以及X射线单晶衍射表征。荧光测试发现:化合物1~3在393nm处有发射峰,该荧光来源于苯并噻唑环中电子的π…π跃迁。     

层状有机-无机杂化钙钛矿(C7H12N2)PbBr4的合成、结构及发光性质

通过向杂化体系中引入特殊的有机配体2-（2-氨基乙基）吡啶,利用溶液冷却技术,合成了一种二维层状有机-无机杂化钙钛矿结构材料的化合物(C7H12N2)PbBr4的晶体。 X射线单晶衍射结果表明,化合物(C7H12N2)PbBr4的单晶结构属于正交晶系,Pbca空间群,a=1.702 3 nm,b=0.828 9 nm,c=2.022 4 nm,Z=8。 无机部分是由共顶点的PbBr6金属卤化物八面体组成的二维平面片层。 采用了相对扭曲构型的有机胺阳离子与二维无机片层通过氢键作用组成了杂化钙钛矿结构。 对其光学性质进行了测试。荧光光谱的特征发射峰出现在422 nm处。     

Preparation, luminescent, structural and electrical properties of Langmuir-Blodgett films of new organomercurial acetylide complex/heteropolyoxometalate hybrid composites

A new family of organometallic/inorganic nanohybrid Langmuir-Blodgett (LB) films consisting of rigid-rod organomercury acetylide complex (OMA) as the π-conjugated organometallic composite and heteropolyacid salts MPA (MPA = K₃PMo₁₂O₄₀, K₅BW₁₂O₄₀, Na₅IMo₆O₆₂) of the Keggin and Anderson structures as the inorganic composite, were prepared and characterized by π−A isotherms, UV−Vis absorption spectra, fluorescence spectra, scanning tunneling microscopy, atomic force microscopy imaging and low-angle X-ray diffraction. Our experimental results indicate that steady Langmuir and LB films are formed in pure water and heteropolyacid salt subphases. Luminescence spectra of hybrid LB films show that MPA can quench the emission of OMA to some extent. These alkynylmercury(II) based LB films display interesting electrical conductivity behavior. They all show decent electrical conductivity, and the tunneling current amounts to ±100 nA when the voltage is set at ±3 ∼ ±5 V.     

Preparation, luminescence and photoelectric properties of Langmuir-Blodgett films of alkynylplatinum(II)-zinc(II) porphyrinate/heteropolyoxometalate hybrid composites

A new class of organometallic/inorganic hybrid Langmuir-Blodgett (LB) films, consisting of rigid-rod alkynylplatinum(II)-zinc(II) porphyrinate complex (OMA) as the π-conjugated donor-acceptor-type molecule and tungsto(molybdo)phosphoric heteropolyacids (HPA) (HPA = H₃PMo₁₂O₄₀ and H₃PW₁₂O₄₀, abbreviated as HPMo₁₂ and HPW₁₂, respectively) of the Keggin structure as the inorganic component, were prepared and characterized by π-A isotherms, UV-vis absorption and luminescence spectra, low-angle X-ray diffraction, scanning tunneling microscopy and surface photovoltage spectroscopy. Our experimental results indicate that stable, well-defined and well-organized Langmuir and LB films have been formed in pure water and heteropolyacid subphase. They typically have a highly organized lamellar structure in which a monolayer of HPA is most likely embedded inside the OMA molecular space formed by long chains of PBu₃. Luminescence spectra of these hybrid LB films show that HPMo₁₂ and HPW₁₂ can enhance the emission of OMA to some extent. These LB composites show good photovoltage responses and a photovoltage of 79 μV can be obtained for the OMA/HPMo₁₂ system when it is excited by light. The monolayer LB films on ITO wafer can also display interesting electrical conductivity.     

Langmuir-Blodgett films of p-terphenyl in different matrices: evidence of dual excimer

Langmuir-Blodgett (LB) films at different mole fractions of p-terphenyl have been prepared using two different matrices, viz., stearic acid (SA) and polymethyl methacrylate (PMMA). Multilayered LB films have been formed by changing various LB parameters namely, mole fraction of mixing, changing the number of layers as well as also the different surface pressure of lifting. The spectroscopic characteristics of mixed LB films, solution and microcrystal have been compared using UV-vis absorption and steady state fluorescence spectroscopy. Change of planarity of TP molecules are occurred while going from solution to solid states/films. Fluorescence spectra of the mixed LB films reveal intense excimeric emission in the mixed LB films with D1 excimer peak at 397 nm and D2 excimer peak at 412 nm. Various LB parameters namely changing the number of layers as well as the different surface pressure of lifting played important roles in the formation of dual excimeric sites in the mixed LB films.     

稀土三酞菁夹心化合物混合LB膜的研究

将不对称三明治型夹心化合物(Pc)Dy[Pc(OC₈H₁₇)₈]Dy[Pc(OC₈H₁₇)₈]与硬脂酸混合成膜，表面压-面积（π-A）曲线表明形成了稳定的单层膜，由透射电子显微镜（TEM）观察,表明硬脂酸的加入有效地改善了分子的聚集行为，分子形成了取向高度有序的结构。用紫外-可见光谱、偏振紫外可见光谱、低角X射线衍射等对LB膜进行了研究，发现该取代稀土三酞菁分子在气/液界面上长链向上伸展，分子之间均以面对面（face-to-face）排列，以一边接触（edge-on）方式取向,大环平面与基片夹角约为52°，每层厚度为2.41 nm。     

双核锌配位化合物[Zn(C15H8O7S)(DMSO)]2•H2O的合成和晶体结构及光致发光性能研究

以白杨素为先导化合物, 对其进行磺化, 磺化衍生物与锌络合, 在含水10%的二甲基亚砜(DMSO)溶液中重结晶, 得双核锌配位化合物[Zn(C₁₅H₈O₇S)(DMSO)]₂•H₂O. 采用IR, ¹H NMR, DSC-TGA, 元素分析和X射线单晶衍射法对标题化合物进行了表征和晶体结构测定. 标题化合物属正交晶系, 空间群Pbcn, Zn(II)的配位数为5, 配位原子均为氧原子, 每个五配位的锌都具有四方锥型的配位构型, 被2个配体5-羟基氧负离子-7-羟基黄酮-6-磺酸根的5-羟基氧负离子桥联, 形成了一个中心Zn₂O₂的菱形平面. 水溶性白杨素黄酮配体与Zn(II)通过氢键、π-π堆积和配位作用自组装形成了一个三维结构的超分子化合物. 差示扫描量热分析(DSC-TGA)结果表明,标题化合物配体骨架分解温度为518.26 ℃. 同时, 标题化合物固体具有较强的光致发光现象, 在λ_ex＝423 nm条件下可发出λ_em＝488 nm的黄色荧光, 并对其发光机制进行了探讨.     

Synthesis of cadmium sulphide in pure and mixed Langmuir-Blodgett films of n -octadecylsuccinic acid

Cadmium sulphide (CdS) nanoparticles were grown by the reaction of sodium sulphide (Na₂S) with Langmuir-Blodgett (LB) films of cadmium salts ofn-octadecylsuccinic acid (ODSU) and with LB films of ODSU in mixtures of octadecylamine and octadecyl alcohol. The results indicate that heterogeneous nucleation and aggregation in the pure ODSU LB films due to processes like Ostwald ripening are destabilized by the presence of the long-chain amine and alcohol in mixed systems. CdS nanoparticles in the LB films were monitored by UV-visible absorption spectra, which allow an estimation of the size of the particles. The morphology, size and nature of the nanocrystallites formed depend on whether the sulphidation was done on the pure film or in the mixed films. It is seen that particles of size around 1.6 nm were formed in ODSU/octadecylalcohol and ODSU/ octadecylamine mixed LB films while in pure ODSU films the size was about 2.7 nm. These films showed typical needle-shaped structures, as observed by the optical microscopic technique. Mean size and morphology were confirmed by transmission and scanning electron microscopy, while selective area electron diffraction patterns showed six-fold symmetry and indicated that the CdS crystals grow epitaxially with respect to the monolayer. Further, the crystallisation enhanced in the mixed LB films showed a characteristic zinc oxide (Wurtzite) structure compared with the pure ODSU matrix.     

A purely organic D-π-A-π-D emitter with thermally activated delayed fluorescence and room temperature phosphorescence for near-white OLED

A purely organic D-π-A-π-D type emitter showing thermally activated delayed fluorescence(TADF) and room temperature phosphorescence(RTP) was designed and synthesized by utilizing the benzophenone as an acceptor and the N-phenyl-2-napthylamine as a donor moiety.It exhibits considerable TADF character in doped PMMA film and room temperature phosphorescence with a long lifetime of 74 ms at466 nm in solid state.The devices with the configuration of ITO/Mo_2 O_3(4 nm)/mCP(30 nm)/mCP:x wt%NP2 BP/TmTyPB(60 nm)/LiF(1.5 nm)/AI(100 nm) were prepared by vacuum evaporation to explore their electroluminescent performance.Intere stingly,the non-doped device has obtained near-white emission with a fluorescence emission peak at 475 nm and a phosphore scence emission peak at 563 nm having the CIE coordinate of(0.23,0.32) and the maximum external quantum efficiency of 1.09%.