溶剂手性转移法制备超支化共轭聚合物手性荧光纳米粒子

通过Suzuki缩合反应制备了一系列新型不同超支化结构的9,9-二辛基芴-联二噻吩交替共聚物(HF8T2s).以手性溶剂(R)-(+)-/(S)-(-)-柠檬烯为手性源,在三氯甲烷/((R)-(+)-或(S)-(-)-)柠檬烯/甲醇混合溶剂体系里,通过溶剂手性转移技术,制备了分别以三苯胺、三苯基苯和螺二芴为支化单元的超支化聚(9,9-二辛基芴-联二噻吩)手性荧光纳米粒子.在混合溶剂中形成的荧光纳米粒子的手性来源于手性溶剂(R)-(+)-/(S)-(-)-柠檬烯.以三苯胺为支化单元时,支化单元的含量为4.56%时聚合物的手性信号最强,支化单元的含量为6.76%时聚合物的手性信号消失.以三苯基苯和螺二芴为支化单元时,支化单元的含量分别为1.85%(三苯基苯)和1.78%(螺二芴)时聚合物的手性信号最强,支化单元的含量较高(三苯基苯:4.68%和6.56%,螺二芴:4.54%和6.54%)时聚合物的手性信号消失.以超支化聚合物HF8T2-TRA2(三苯胺为支化单元,支化单元含量为1.90%)为例,考察了超支化聚合物重复单元浓度、弱溶剂的种类、弱溶剂与手性溶剂比例和(R)-(+)-柠檬烯与(S)-(-)-柠檬烯比例对超支化聚合物圆二色谱光谱强度的影响.当超支化聚合物重复单元浓度为5.0×10-5mol/L,使用甲醇为弱溶剂,三氯甲烷/((R)-(+)-或(S)-(-)-)柠檬烯/甲醇之间的配比为0.3∶1.8∶0.9(V/V/V)时,超支化聚合物圆二色谱光谱强度最强.在三氯甲烷/((R)-(+)-或(S)-(-)-)柠檬烯/甲醇(0.3∶1.8∶0.9(V/V/V))混合溶剂中,聚合物重复单元浓度为5.0×10-5mol/L,超支化聚合物在350～550 nm有较强的紫外吸收,在450～700 nm有较强的荧光发射,组装成的荧光纳米粒子尺寸约为500～2000 nm.     

含苯并硒二唑聚咔唑/芴类共轭聚电解质及其前驱体的合成与性能研究

采用Suzuki偶合反应合成了一系列新型的咔唑、芴和2,1,3-苯并硒二唑的共聚物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-双(N,N-二甲基胺丙基)芴](PCzN-BSeD)及其相应的聚电解质衍生物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-(双(3′-(N,N-二甲基)-N-乙基铵)丙基)芴]二溴(PCzNBr-BSeD).在聚咔唑和芴中引入不同比例的2,1,3-苯并硒二唑(BSeD)单元,引起了由咔唑和芴链段向窄带隙苯并硒二唑(BSeD)单元有效的能量转移.通过对聚合物电致发光性能的研究,发现用聚(3,4-亚乙基二氧基噻吩)(PEDOT)或聚(3,4-亚乙基二氧基噻吩)/聚乙烯咔唑(PEDOT/PVK)作为空穴传输层时,器件的性能相差不大,表明咔唑的引入较明显的改善了聚合物的空穴注入性能.而且几乎所有的聚合物用高功函数铝作阴极的器件和用钡/铝作阴极的器件具有相近的发光性能,表明这类聚合物具有良好的电子注入性能.     

基于荧光共轭聚合物的金属离子传感研究

设计合成了一系列结构相似的共轭主链含5%苯并噻二唑结构单元及侧链带胺类金属离子螯合基团的阴离子型水溶性共轭聚合物PFA, PFBTA和PFBTNA, 并对它们在不同极性溶剂中的光物理性质进行了研究. 利用分子主链含适量苯并噻二唑共聚单元的聚芴衍生物聚集态不同荧光光谱及颜色发生显著变化这一特性, 研究了这一系列水溶性聚芴衍生物在水/甲醇(9/1)溶液中对金属离子的荧光响应过程. 结果表明, 金属离子不仅能通过能量及电荷转移猝灭聚合物荧光, 还可以通过静电相互作用力使聚合物聚集态发生改变, 进而影响聚合物的光学性质. 同时分子链上引入金属离子螯合基团能够显著提高体系的检测灵敏度, 聚合物PFBTA和PFBTNA可以特异性识别Cu²⁺离子, 并且可做为其它金属离子的广谱型比色法检测材料.     

聚芴基苯并唑类共聚物的合成和光物理性能

通过溶液缩聚法合成了一系列不同组分的无规共聚物--聚对苯撑苯并二噁唑-co-聚(9,9-二辛基芴苯并二噁唑)(PBO-co-PBOF).利用X射线衍射、紫外-可见光吸收光谱、光致荧光光谱研究了不同组分和结构变化对聚合物形态和光物理性能的影响.结果表明:聚合物主链上辛基芴基团的引入使聚合物结构从晶态转变为非晶态.共聚物分...     

含电子给体-受体的交叉共轭聚合物合成及其离子传感性能

在芴苯结构主链中引入苯并噻唑作为电子受体、侧链上引入N,N-二丁基苯胺作为电子给体,通过Suzuki反应制备了新型交叉共轭聚合物P1,同时合成主链中不含苯并噻唑的芴苯类共聚物P2作为对比;对两者的化学结构和光物理性质进行了表征,并研究了聚合物对离子的光学传感性能.实验和模拟计算结果均表明,P1中存在着强的分子内电荷转移效应;引入电子给体和受体(D-A)能够有效地调控交叉共轭聚合物的光学特性,这种D-A型交叉共轭聚合物是一类潜在的具有荧光增强性能的化学传感材料.     

主链含有非共轭结构的聚芴类蓝光聚合物的合成与性能研究

通过Suzuki偶合反应合成出了主链中含有非共轭烷氧基组分(-O-CH2-CH2-CH2-CH2-O-)的聚芴类衍生物聚- 2,7-(9,9-二辛基芴)-co-4,4’-丁氧基二苯(PFP)和聚-2,7-(9,9-二辛基芴)-co-4,4’-丁氧基二苯-co-N-苯基-4,4’-二苯胺(PFTP11)并通过相同的条件合成出主链由芴和三苯胺交替相连的聚合物聚-2,7-(9,9-二辛基芴)-co-N-苯基-4,4’-二苯胺(PFTPA)作为参比材料. 通过1H NMR和FT-IR分析对这些聚合物的化学结构进行了表征. 这三种聚合物在常用的有机溶剂中具有很好的溶解性, 可通过溶液加工的方式制备聚合物薄膜. 这些聚合物均具有较高的热分解温度(＞400 ℃), 聚合物PFP具有较高的玻璃化转变温度(～130 ℃)而PFTP11和PFTPA则未出现明显的玻璃化转变过程. 通过对聚合物的吸收特性进行测试得知它们具有较大的光学带宽(2.89～3.29 eV). 所有聚合物在固体薄膜状态下均发射出蓝色荧光, PFP, PFTP11和PFTPA的最大PL发射分别位于425, 437和440 nm. 通过对其电化学性能进行测试可知由于三苯胺基团的引入聚合物的HOMO能级明显提高, 这意味着聚合物的空穴传输能力得到了有效的改善.     

含噻吩单元的硅芴共聚物的合成及其蓝色电致发光性能

将少量(摩尔分数为1%—3％)含噻吩的窄带隙单体和宽带隙硅芴单体进行共聚, 合成了聚{9,9-二己基-3,6-硅芴-co-[2,5-二(2-甲基苯撑-4-基)-噻吩]}和聚{9,9-二己基-3,6-硅芴-co-[2,5-二(2-苯撑-4-基)-噻吩]}两类硅芴共聚物, 通过紫外-可见吸收光谱、光致发光光谱, 并制作聚合物发光二极管器件测试电致发光光谱等手段, 系统表征了两类硅芴共聚物材料的性能. 实验结果表明, 噻吩的加入形成了新的蓝色发光中心, 并且实现了从硅芴链段到含噻吩发光中心的有效能量转移. 通过增加发光中心结构的空间位阻来减小其共轭程度, 可以使聚合物的PL和EL光谱发生较大蓝移. 最终得到了效率为0.46%和色坐标(CIE)为(0.19, 0.16)的蓝光LED器件.     

基于1-(4-己氧)苯和2,4,6-三苯基-1,3,5-三嗪功能化芴单元的聚合物蓝光材料的合成与表征

以聚(9,9-二己烷芴)(1)和聚(9,9-二(1-(4-己氧)苯)芴)(2)作为参照物,通过Suzuki偶联反应合成了侧链9位碳含有4-己氧基苯和2,4,6-三苯基-1,3,5-三嗪单元的芴共聚物3.聚合物1,2和3固体粉末的5%质量热损失温度分别是274,318和401℃,玻璃化转变温度分别是91,120和139℃.聚合物1,2和3在甲苯溶液中的最大吸收峰和荧光发射峰分别在380和435 nm.从聚合物1到聚合物3,薄膜的荧光发射最大半峰宽逐渐降低.大体积刚性吸电子2,4,6-三苯基-1,3,5-三嗪基团的引入,使聚合物1,2和3的热稳定性、蓝光发射的色纯度和光谱稳定性逐渐提高,不同工作电压驱动下聚合物3稳定的电致发光光谱进一步证明了这一点.聚合物1,2和3的最高占有轨道能级分别为-5.72,-5.95和-5.96eV,最低未占有轨道能级分别为-2.70,-2.39和-2.43 eV.聚合物1,2和3的三线态能级分别为2.82,2.81和2.97 eV.聚合物1,2和3的单线态-三线态能级差分别是0.32,0.32和0.15 eV.4-己氧基苯的引入使聚合物的能隙变宽,而吸电子的2,4,6-三苯基-1,3,5-三嗪的引入使聚合物单线态-三线态能级差依次减少.聚合物1,2和3粉末均易于形成非晶薄膜.聚合物3粉末的有序性介于聚合物1和2之间,聚合物2侧链的烷氧基苯有助于提高固体粉末有序形态的多样化.综合结果表明,侧链含有刚性4-己氧基苯和2,4,6-三苯基-1,3,5-三嗪基团的无规共聚物3具有更佳的综合光电性质.     

三氟化硼乙醚溶液中卤代芴的电化学聚合

在三氟化硼乙醚(BFEE)溶液中9-溴芴和9,9-二氯芴可以直接阳极氧化制备聚(9-溴芴)和聚(9,9-二氯芴).单体在BFEE中的起始氧化电位远低于在乙腈体系中的起始氧化电位.聚(9-溴芴)和聚(9,9-二氯芴)均可溶于强极性有机溶剂,如二甲基亚砜、四氢呋喃等,并分别表现出良好的蓝色和黄绿色发光性能,其电导率测定为10-1S/cm.红外光谱和核磁共振波谱表明聚合反应主要发生在2,7位.     

端基为橙光基团的聚芴合成和发光性质

含溴橙光化合物与双(三环己基膦)钯(0)进行氧化加成反应,合成了相应的芳基钯(Ⅱ)配合物.在加热条件下,该配合物可以引发AB型芴单体聚合,得到端基为橙光芳基基团的聚芴共轭聚合物.含溴橙光化合物与不同配体钯(0)配合物组成催化体系,原位引发聚合,同样可以制备上述端基结构明确的共轭聚合物.其中,以三(邻甲基苯基)膦或卡宾化合物为辅助配体时,室温下即可引发AB型芴单体进行催化剂转移聚合.卡宾化合物为辅助配体时,可以获得Mn为7.48×10~4的高分子量聚芴.MALDI-TOF分析证实,聚合物的一个端基是来自催化剂钯配合物中的橙光芳基基团,另一端基为Br/H原子.聚合物光致发光(PL)光谱主要表现为聚芴单元的蓝色荧光发射.电致发光(EL)光谱表明,聚合物在低分子量时表现为橙红光发射,而在高分子量时,能够得到白光发射.在数均分子量Mn为7.48×10~4时,聚合物可实现纯白光发射,国际色坐标CIE为(0.31,0.32).     

New π‐Conjugated Polymers Containing 1,3,5‐Triazine Units in the Main Chain: Synthesis and Optical and Electrochemical Properties of the Polymers

Summary: Three new soluble π‐conjugated polymers containing 1,3,5‐triazine units in the main chain, Pa–Pc, were synthesized. The polymers showed optical properties in solution that were mainly dependant on the properties of the substituting R groups, on the triazine ring. Hence, Pa and Pb (R = H and  OCH₃, respectively) showed blue photoluminescent (PL) emission with high quantum yields (QY) even in polar solvents, whereas Pc (R = N,N‐dimethylamino) gave green‐blue PL emission with very low QY. The PL spectra of the polymers in solution were concentration and polarity dependent, which suggested the formation of an exciplex.

The three new soluble π‐conjugated polymers containing 1,3,5‐triazine units in the main chain synthesized here.     

An X‐shaped π‐conjugated polymer comprising of fluorene units and anthracene units with high efficiency. Synthesis and optical and electrochemical properties

A new X‐shaped π‐conjugated monomer comprising of fluorene units and anthracene units was synthesized, and it was used to fabricate the new X‐shaped π‐conjugated polymers and investigate the properties of the new polymers. Using different molar ratios between such monomer and a fluorene monomer gave three polymers that showed higher absolute PL quantum yields than the linear polyfluorene (PF) in the solid state. After thermal annealing at 200 °C for 4 h, the linear PF showed an additional bathochromic emission at about 550 nm, whereas such red‐shifted emission was fully eliminated for the X‐shaped polymers. The electroluminescent devices based on the X‐shaped polymers with a configuration of ITO/PEDOT:PSS/polymer/LiF/Ca/Al displayed blue emission with low turn‐on voltage and high brightness. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5616–5625, 2008     

Synthesis and characterization of light‐emitting oligo(p‐phenylene‐vinylene)s and polymeric derivatives containing three‐ and five‐conjugated phenylene rings

Several series of light‐emitting oligo(p‐phenylene‐vinylene)s (BIII and BV series containing three‐ and five‐conjugated phenylene rings) with various side groups and end groups attached to the cores were synthesized and characterized. The analogous PBV polymers, derived from the BV series, were also synthesized and investigated. Blue and greenish light emissions were observed in the photoluminescence (PL) and electroluminescence (EL) spectra of the blend and pure films with these π‐conjugated structures. In contrast to the three‐conjugated ring oligomers, the five‐conjugated ring derivatives (oligomers and polymers) had larger maximum emission wavelength values of PL and EL emissions. Mesomorphism was introduced into the BV series by the replacement of three‐conjugated rings (BIII series) with five‐conjugated phenyl cores (BV series). The liquid‐crystalline properties of the BV series with end groups (on both end rings) were better than those of analogous BV‐OC₈ without end groups. Polarized PL emissions were obtained by the alignment of liquid‐crystalline phase in rubbing cells. Upon heating, different PL emission wavelengths and intensities were observed in various phases. Not only the solubility and thermal properties but also the PL and EL properties could be effectively adjusted by the attachment of flexible alkoxy groups either on the central rings or on both end rings of the conjugated cores. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 783–800, 2006     

水体系中含卟啉基团的两亲高分子的自组装行为和性质的研究

在文中合成了两种不同的卟啉单体5-(4-acryloyloxyphenyl)-10,15,20-tris(4-carboxylphenyl)porphyrinate zinc(Ⅱ)(ZnAOTCPP)和5-(4-acrylo-yloxyphenyl)-10,15,20-tris(4-methoxycarboxylphenyl)porphyrinate zinc(Ⅱ)(ZnMeAOTCPP),它们分别与丙烯酰胺(Acrylamide,AM)聚合得到含有卟啉基团的两亲高分子.与对应的单体相比,含有三羧酸卟啉基团的高分子在水中形成了一个新的紫外吸收峰和一个新的荧光发射峰,而含有三羧酸甲酯卟啉基团的高分子除此之外在更长波的方向上还另外出现了一个新的紫外吸收峰和一个新的荧光发射峰.随着高分子水溶液浓度的提高,高分子中卟啉基团的光谱性质的变化趋势显示高分子在水中的自组装行为可以分为分子间缔合和分子内缔合的两种情况.此外,实验结果显示含有三羧酸甲酯卟啉基团的高分子相对于含有三羧酸卟啉基团的高分子更加有利于卟啉缔合物的形成.     

Novel Bipolar Conjugated Polymer Containing Both Triphenylamine and Oxadizole Units

A novel bipolar conjugated polymer containing triphenylamine and 1,3,4-oxadiazole units was synthesized by Suzuki reaction.Its structure and properties were characterized by NMR,IR,UV-Vis,PL spectroscopy and electrochemical measurement. The photoluminescent spectroscopy and cyclic voltammograms measurement demonstrated that the resulting polymer shows blue emission (477 nm) and possesses both electron and hole-transporting property.     

Synthesis of Pyrene‐based Planar Conjugated Polymers and the Regioisomers by Intramolecular Cyclization

Several planar conjugated polymers and model compounds containing pyrene units are synthesized. The precursor polymers and model compounds are obtained through the Pd(0)‐catalyzed Suzuki reaction, then the planar structure is formed through intramolecular cyclization in the presence of acid. We investigate the regioisomers in intramolecular cyclization reaction by using model compounds, suggesting that the syn‐ and anti‐structures are formed in ladder‐type polymer LP1 , and the syn‐structure is more easily formed in LP3 . The planar conjugated polymers and model compounds show untypical features of ladder‐type polymers, they display broad absorption and blue or blue‐green emission in solution, and interchain π‐π stacking in film still occurs. Moreover, the new polymers and model compounds are characterized by nuclear magnetic resonance (NMR) spectroscopy, gel‐permeation chromatography (GPC) and cyclic voltammetry (CV).     

New poly(p‐phenylene vinylene) derivatives with two oxadiazole rings per repeat unit: Synthesis,photophysical properties,electroluminescence, and metal ion recognition

Two new poly(p‐phenylene vinylene) derivatives OX1‐PPV and OX2‐PPV bearing two 1,3,4‐oxadiazole rings per repeat unit and a fully conjugated backbone with solubilizing dodecyloxy side groups were synthesized and investigated. The amorphous conjugated polymers had glass‐transition temperature values of 60–75 °C and emitted intense blue or greenish‐blue light in solution with photoluminescence (PL) emission maxima at 379–492 nm and PL quantum yields of 0.41–0.52. In the solid state they emitted yellowish‐green light with PL emission maxima at 533–555 nm. Cyclic voltammetry showed that both conjugated polymers had reversible reduction and irreversible oxidation, making them n‐type materials. The electron affinity of OX2‐PPV was estimated as 2.85 eV whereas that of OX1‐PPV was 2.75 eV. Yellow electroluminescence (EL) was achieved from single‐layer light‐emitting diodes of OX2‐PPV with an EL emission maximum at 555 nm and a brightness of 70 cd/m². Polymer OX2‐PPV, which was functionalized with 2,6‐bis(1,3,4‐oxadiazole‐2‐yl)pyridine, demonstrated sensitivity to various metal ions as a fluorescence‐mode chemosensor. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2112–2123, 2004     

Synthesis and Properties of Highly Photoluminescent and Electrochemically Active Polymers Containing 2‐Pyrazoline Units in the Main Chain

Summary: Two new polymers containing 2‐pyrazoline units in the main chain were synthesized for the first time by a Suzuki polycondensation between a 2‐pyrazoline monomer and aryl diboronic esters. The polymers showed high photoluminescence (PL) in both the solution and the solid state; quantum yields of PL in toluene were higher than 76%. Thermogravimetric analysis and cyclic voltammetry showed that the polymers had high thermal stability and good reversibility under electrochemical oxidation.

New polymers ( 2 and 3 ) with strong photoluminescence and good reversibility under electrochemical oxidation were synthesized here.     

聚芴主链含D-A型萘并噻二唑和苯并硒二唑衍生物的红光高分子发光材料

设计合成了新型的含萘并噻二唑（NT）或苯并硒二唑（BS）电子受体单元的D-A型红光掺杂剂,将它们引入到聚芴(PFO)的主链,调节掺杂剂含量,合成了一系列具有“掺杂剂/主体”特性的红光高分子材料含萘并噻二唑衍生物的聚芴(PFR-xNT)和含苯并硒二唑衍生物的取芴(PFR-xBS)。 这些红光高分子的吸收光谱主要表现为聚芴主体的吸收,荧光光谱既有主体聚芴的蓝光峰,也有掺杂剂的红光峰,并且红光峰的相对强度随着掺杂剂含量的增加而增强。 与光致发光光谱不同,这些高分子的电致发光光谱主要表现为掺杂剂的红光发射,并在掺杂的摩尔分数达到1%时实现了主体聚芴向红光掺杂剂的完全能量转移。 其中PFR-10NT和PFR-10BS的单层器件(ITO/PEDOT:PSS/Polymer/Ca/Al)(PEDOT:聚3,4-乙烯二氧噻吩;PSS:聚苯乙烯磺酸)分别实现了电流效率1.61 cd/A,最大发射波长632 nm,CIE色坐标（0.63,0.35）以及电流效率1.10 cd/A,最大发射波长620 nm,CIE色坐标（0.63,0.36）的高效红光发射。     

High quantum yield photoluminescence of new polyamides containing oligo‐PPV amino derivatives and related oligomers

The synthesis and the chemical physical characterization of new photoluminescent (PL) chromophores and polymers are reported. Chromophores (oligo‐PPV symmetric derivatives ending with amino groups) are strong blue emitters with a PL quantum yield of ～70% in dioxane solution. They have been used to prepare polyamides by reaction with aliphatic acyl dichlorides in which emitting and non emitting units are alternated. PL properties of the synthesized polyamides have been evaluated in solution and reveal a strong blue emission (PL quantum yield ～60%), To increase the solubility of these systems, oligomers have been purposely prepared and then characterized. They show a peculiar white emission when excited in DMF solution; to get insight into this interesting behavior, asymmetric monoacetylated chromophores have been prepared as model compounds for the chromophoric end groups of the polyamide chains. The emission spectra of these compounds reveal a broad excimeric yellow emission which is responsible, along with the blue emission of the inner chromophoric units, of the overall white emission of the oligomers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2677–2689, 2009