SYNTHESIS AND OPTICAL PROPERTIES OF POLY (THIENYLACETYLENES)*

3 -Ethynyl-4-(trimethylsilyl)thiophene (1a) and 3 -ethynyl-4-bromothiophene (1 b ) selectivelyundergo acetylene polymerizations in the presence of the MoCl_5- and WCl_6-Ph_3SiH catalysts to give soluble,high-molecular-weight poly(thienylacetylenes) (2) (M_w up to 602000) in high yields (up to 100%). Lighttransmission spectra of THF solutions of 2 continuously red-shift with increasing concentration. Theconcentratochromism shows a logarithmic concentration dependence; that is, the optical transitions of 2 arepredictably tunable by simply changing their concentrations.     

一类新型取代乙炔化合物的合成及表征

用二环己基碳酰亚胺(DCC)和N,N-二甲基吡啶(DMAP)催化法合成了系列功能取代乙炔;与酸催化等法进行比较,DCC／DMAP催化法具有反应条件温和、产率高的优点;用元素分析,IR,^1H NMR和DSC等对它们的结构进行了表征和确认。     

FULLERENE POLYMERS WITH TUNABLE OPTICAL PROPERTIES

Light transmission spectra of THF solutions of poly (C_(60)-co-methyl methacrylate)s andpoly (C_(60)-co-styrene)s continuously red-shift with increasing concentration. Formation offullerene nanoclusters may be responsible for the unusual spectral shift with concentration.It has long been scientists' dream to "tune" material's properties by simple means, and theC_(60)-containing polymers represent such a group of novel materials whose optical propertiesare predictably and reversibly tunable by a simple change in concentration.     

有机/无机杂化钙钛矿(C14H13N2O2)2PbCl4的制备与表征

合成了一种新颖的有机/无机杂化钙钛矿(C14H13N2O2)2PbCl4材料,采用元素分析、红外光谱(FT-IR)、紫外可见吸收光谱(UV-Vis)、透射电镜(TEM)、电子衍射(ED)、紫外可见光声光谱(UV-Vis PAS)和表面光电压谱(SPS)等手段对其分子结构和聚集态、光学性质和光、电特性进行了表征。结果表明,这种材料具有较好的有序性,在紫外光波段同时具有较好的光电响应和光声特性。     

含有手性和发光官能团侧基的聚1-苯基-1-辛炔的合成与性能研究

设计并合成了一系列含手性和发光生色团侧基的聚（1-苯基-1-辛炔）衍生物{-[（C6H13）C=C（C6H4-p-CO2-R）]n-,R=[（1S）-endo]-（-）-冰片基（P3）,（1R,2S,5R）-（-）-薄荷基（P4）,-C6H4-p-（1R,2S,5R）-（-）-薄荷基（P5）,2-萘基（P6）,4-联苯基（P7）}.用WCl6-Ph4Sn作催化剂,成功地制备了这些具有中等产率和高分子量（Mw高达64000）的聚合物.聚合物的结构和性能通过NMR,TGA,UV,CD,PL和EL等分析方法进行了表征.所有聚合物都表现出良好的热稳定性,在N2保护条件下,其失重5%的温度在300～416℃之间.所有聚合物的带隙约为3.0eV.聚合物P4和P5表现出与聚合物链段螺旋性相对应的CD吸收.在UV辐照下,P3～P7的THF溶液均发射强烈蓝光,其最大发射波长位于485nm左右,量子效率均高于20%.聚合物薄膜发射与其溶液发射在相同的光谱区域,并表现出轻微的聚集诱导猝灭.制备了ITO/聚合物：PVK/BCP/Alq3/LiF/Al多层聚合物EL器件,其最大发射波长为487nm.随着侧基的改变,器件的最大亮度和外量子效率也随之发生变化,其中P6表现出最高的外量子效率（0.16%）.EL器件均具有良好的光谱稳定性,其EL最大发射峰几乎不随外加电压的变化而改变.     

含芳杂环的超支化聚合物的合成与性能研究

在紫外光照射的条件下,以CpCo(CO)2为催化剂,通过3,5-双-(4-炔苯基)-4-苯基-1,2,4-三唑和2,5-双-(4-炔苯基)-1,3,4-(噁)二唑的双炔分别与1-辛炔的[2 2 2]环三聚反应,合成了一类含芳杂环的可溶于普通有机溶剂的新型超支化聚合物.采用红外光谱、核磁共振谱、热失重分析、紫外吸收光谱、荧光光谱、循环伏安法等方法对聚合物进行结构表征和性能测试.结果表明,聚合物具有优异的热稳定性,尤其是含三唑的聚合物热失重5%的分解温度在450℃以上;在800℃时,残余碳化率高达75%.在光激发的条件下,这类聚合物在二氯甲烷溶液中发射深蓝光,其荧光量子效率可达80%.电化学测试结果表明,这类含芳杂环聚合物具有较好的电子传输能力.     

Synthesis of polyelectrolytic polyacetylene derivatives by quaternization of poly(pyridylacetylene)

Functional polyacetylenes containing pyridinium side groups（PPyA-MX,X = Br and I） were successfully synthesized.Spectroscopic techniques such as ¹H-NMR,¹³C-NMR,and FTIR spectroscopy were used to characterize the structure of the obtained polymers.The characterization data were well consistent with the expected macromolecular structures.PPyA-MI had good solubility in polar organic solvents and low solubility in water,while PPyA-MBr had good solubility in both polar organic solvents and water.     

反构造原理策略实现高稳定有机发光自由基

To solve the problem of stability of organic luminescence radicals, Li et al. proposed a new kind of organic luminescence radicals with non-Aufbau electronic structure by using donor-acceptor molecular structure. The stability of this kind of radicals was greatly improved and the high luminous efficiency was maintained. Using a non-Aufbau radical as the emission layer of an OLED, the maximum external efficiency of 5.3% has been achieved, which is among the highest efficiencies for pure organic near-infrared electroluminescence. This work has been published online in the Nature Materials in July 22, 2019.     

荧蒽修饰的四苯基乙烯衍生物:分子合成、聚集增强荧光特性及其对苦味酸的高灵敏度检测

由于聚集体和固态发光量子效率高等优点,因此聚集诱导发光（AIE）材料成为光电功能材料研究领域的热点,拓展AIE分子体系始终是这一领域中的关键和基础的科学问题.通过Suzuki-Miyaura偶联这一条件较为温和的反应,将AIE生色团四苯基乙烯（TPE）与荧蒽直接共轭键接,制备得到单荧蒽和双荧蒽修饰的TPE衍生物TPE-FA与TPE-DFA,它们具有聚集增强荧光（AEE）行为,聚集体发射峰值波长分别在477和494 nm,固体薄膜的绝对荧光量子产率高达74.1%和40.4%.它们可以高灵敏地检测苦味酸,荧光猝灭常数大,检出限低于1 μg·g^-1.这两种AEE分子可望用于其它多硝基取代的芳香类吸电子分子的检测.     

PbS纳米粒子与全共轭高分子的自组装膜原位复合及其光电转换性质

无机纳米粒子因其在催化、磁学、光子学等方面的特殊性质而越来越受到关注,纳米粒子粒径及分布可以人为控制,由此能够改变与有机聚合物所形成的纳米复合材料性能,在各种无机纳米粒子／有机聚合物复合材料制备方法中,纳米反应器(Nanoreactor)技术正日益受到关注,与常规的作为化学反应特定场所的化学反应器不同,纳米反应器不是一般的具体的机械设备,