可光固化单体2,7-二溴-9,9-双[4’-(3″-乙基-3″-氧杂环丁烷甲氧基己基氧基)苯基]芴的合成

以芴为原料,经溴代和氧化反应制得2,7-二溴芴酮(3);3与苯酚反应合成2,7-二溴-9,9-双(4’-羟基苯基)芴(4);4与3-(6’-溴己氧基甲基)-3-乙基氧杂环丁烷经醚化反应合成了可光固化单体2,7-二溴-9,9-双[4’-(3″-乙基-3″-氧杂环丁烷甲氧基己基氧基)苯基]芴,总收率67%,其结构经1H NMR,13C NMR和元素分析表征。     

2-芳基-3,4-二氮杂芴酮和2-芳基-3,4-二氮杂螺二芴衍生物的合成

水合茚三酮与芳甲基酮、水合肼缩合环化制得2-芳基-3,4-二氮杂芴酮(2); 2经还原得2-芳基-3,4-二氮杂芴(3).2与2-溴联苯格氏试剂反应得到中间体叔醇(4); 4在酸性条件下关环合成了2-芳基-3,4-二氮杂螺二芴,其结构经1H NMR,13C NMR和元素分析表征.     

2,6-二甲基二苯并噻吩加氢脱硫中间体的合成

以2-溴代-3-甲基环己酮和2-溴代-5-甲基环己酮混合物及2-甲基苯硫酚为原料,经耦合、环化及纯化制得1,2,3,4-四氢-2,6-二甲基二苯并噻吩(3);3在三氟乙酸中经锌粉还原合成了1,2,3,4,4a,9b-六氢-2,6-二甲基二苯并噻吩(4).3和4的结构经1H NMR,13C NMR和GC-MS确证.     

串联的铜、钯催化偶联-环化合成二芳胺基芴

发展了一种由串联的铜、钯金属催化偶联-环化合成二芳胺基芴类衍生物的新方法.取代的碘苯与甲基和溴原子互为邻位的苯胺在铜催化下反应生成溴代甲基三苯胺,然后与邻氯苯基硼酸在钯催化下发生Suzuki偶联反应,最后在NHC-Pd催化下发生C(sp3)—H键活化-环化反应.方便地合成了2位,尤其是3位取代的二芳胺基芴类化合物,且均获得了不错的收率.所有化合物均通过了1H NMR,13C NMR,HRMS,IR,紫外和荧光等手段的表征.对其中两个具有代表性的二芳胺基芴的结构运用二维核磁共振技术进行了解析.     

4-[2-(9,9-二辛基-9H-芴-2-)乙烯基]苯胺的合成及其光学性质

以2-溴芴、溴代正辛烷和对硝基苯乙烯为主要原料,通过烷基化反应、Heck反应和还原反应合成了新化合物4-[2-(9,9-二辛基-9H-芴-2-]乙烯基)苯胺(5),其结构经1H NMR和IR表征。应用UV-Vis和荧光光谱初步探讨了5的光学性质。     

9,9-二甲基-2-(N-联苯基)氨基芴的合成

以芴为原料,苄基三甲基三溴化铵为溴化试剂,室温下在甲醇和二氯甲烷中溴化得到2-溴芴,然后以四氢呋喃为溶剂,在叔丁醇钾作用下与碘甲烷反应合成9,9-二甲基-2-溴芴,最后与4-联苯胺通过Buchwald-Hartwig偶联反应合成目标化合物9,9-二甲基-2-(N-联苯基)氨基芴,总收率为56.0%～62.4%。通过1HNMR、13CNMR、MS、IR和元素分析确证了其结构。     

6-溴-7-异丙基-1,10-二甲基-1,2,3,4-四氢蒽-1-羧酸的合成

以脱氢松香酸为原料,经酯化、溴代、氧化、异构化、水解等反应,合成了一种新型的四氢蒽羧酸类衍生物———6-溴-7-异丙基-1,10-二甲基-1,2,3,4-四氢蒽-1-羧酸,其结构经1H NMR,13C NMR,MS和元素分析表征。     

N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二胺基苯基)咔唑的合成方法及表征

以2,7-二溴咔唑为原料经过N-烷基化、Suzuki偶联反应、Buchwald-Hartwig偶联反应合成了有机发光二极管(OLED)空穴传输材料N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二胺基苯基)咔唑,利用NMR、IR和熔点等分析方法对产物结构进行了表征,并通过TG、UV-Vis及荧光光谱研究了物质的热稳定性和光学性能。     

2,7-二溴-4-氨基芴的合成及其光学性质

以芴(1)为原料,通过溴代、硝化、还原反应合成了2,7-二溴-4-氨基芴(4),其结构经1H NMR,13C NMR,IR和ESI-MS确证。分别对溴化、硝化和还原反应条件进行优化。结果表明:在最佳溴化反应条件[CHCl3为溶剂,Cu Br2为催化剂,1 90 mmol,n(1)∶n(Cu Br2)∶n(Br2)=1.0∶0.025∶2.89,于0℃反应24 h]下,溴化产物2,7-二溴芴(2)的产率93.8%;在最佳硝化反应条件[2 30 mmol,混合酸(85%硝酸+96%硫酸)为硝化试剂,n(2)∶n(HNO3)=1.0∶4.6,于70℃反应1 h]下,硝化产物2,7-二溴-4-硝基芴(3)的产率94.7%;在最佳还原反应条件(3 30 mmol,Zn/Ca Cl2为还原剂,回流反应4 h)下,4的产率89.5%。运用UV-Vis和荧光光谱初步研究了4的光学性质。结果表明:4的λmax为352.4 nm;在352.4 nm波长激发下,4的λem位于388.4 nm和412.2 nm,光带隙低至2.66 e V。     

超声波合成2，7-二溴-9，9-二烷基芴

以2,7-二溴芴(1)和溴代烷(2)为原料,二甲亚砜为溶剂,四丁基溴化铵为相转移催化剂,超声波辐射合成了3个2,7-二溴-9,9-二烷基芴(3),其结构经1H NMR,IR,MS和元素分析表征.考察了超声波辐射时间和辐射功率对反应的影响,结果表明,在1 16 mmol,n(1):n(2)=1:1,于45 W辐射反应1 h的反应条件下,3的收率达92%.     

新型含芴基的富勒烯衍生物的合成

以2,7-二溴芴酮为起始原料,经Suzuki偶合、腙化和1,3-偶极环反应合成了3种新型的含芴基的富勒烯衍生物,其结构经UV-Vis,1H NMR,13C NMR,FT-IR和MALDI-TOF-MS表征。     

Preparation and near-infrared optical limiting property of fluorene-containing functional polyacetylene

A novel functional polyacetylene containing fluorene group as a pendant,poly（2-（p-methylstyrene）-7-acetylene-9,9-dioctyl-fluorene）, was synthesized in moderate yield by[Rh（nbd）Cl]₂-Et₃N catalyst.The structures and properties of monomer and polymer were characterized and evaluated with FTIR,NMR,UV-vis,GPC and Z-scan,respectively.The results show that the incorporation of fluorene into polyacetylene has endowed the resultant polymer with well optical limiting properties for laser at wavelength 780 nm based on two-photon absorption mechanism.     

New fluorene‐based copolymers containing oxadiazole pendant groups: Synthesis,characterization, and polymer stability

A series of fluorene‐based copolymers containing hole blocking/electron transporting diphenyloxadiazole units were synthesized by means of Suzuki‐Miyaura coupling of selected aromatic dibromo‐ and diboronato‐ derivatives catalyzed with a Pd(PPh₃)₄ catalyst. All of the copolymers with various composition of main‐chain units were characterized by SEC chromatography, NMR, UV–vis, fluorescence and IR spectroscopy, and DSC. The emission stability of fluorene copolymers was improved by the replacement of alkyl groups on the C‐9 carbon of fluorene with aryl groups or by the incorporation of anthracene units into the copolymer main chain. A comparison of luminescence properties of pristine and annealed thin layers of studied copolymers was performed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4532–4546, 2009     

Phenol side‐groups‐containing fluorene polymer synthesized by catalytic oxidative polymerization

Catalytic oxidative polymerization (OP) of 4,4'‐(fluorene‐9,9‐di‐yl)diphenol (FDP), possessing both phenol and fluorene rings in its structure, was carried out in different organic solvents. Schiff base polymer‐copper (II) complex and hydrogen peroxide were used as a catalyst and an oxidizing agent, respectively. The structure of poly (4,4'‐(fluorene‐9,9‐di‐yl)diphenol) (PFDP) was confirmed by UV–vis, FT‐IR, NMR spectroscopies. Further characterization was conducted by means of thermogravimetric analysis (TGA), DSC, XRD, scanning electron microscopy (SEM), cyclic voltammetry (CV), and conductivity measurements. PFDP showed the optical band gap of 3.09 eV, the emission maximum at 335 nm, and the HOMO level of ?5.75 eV. Copyright © 2010 John Wiley & Sons, Ltd.     

电致变色/电控荧光双功能聚合物的合成及性能

将电活性双胺单体4,4'-二氨基二苯醚与1,2,4,5-环己烷四甲酸二酐共聚, 得到电活性聚酰胺酸聚合物. 再通过后功能化方法, 采用酰胺化反应将2-氨基芴引入到聚合物结构中, 合成了荧光聚合物. 通过核磁、 红外和凝胶渗透色谱证实了聚合物的结构. 该聚合物在0~0.8 V的电压下展示出可逆的电化学活性. 在利用电压改变苯胺齐聚物链段的氧化状态的过程中, 聚合物薄膜发生了明显的颜色变化, 展现出良好的电致变色性质. 荧光性质随着施加电压的改变而变化, 展现出优异的电控荧光特性.     

Synthesis, structure, and photophysical and electrochemical properties of a pi-stacked polymer

Dibenzofulvene (DBF) was polymerized using anionic initiators to afford a vinyl polymer. Oligo(DBF)s having from two to eight side-chain fluorene moieties bearing different chain-terminal groups were isolated by preparative size-exclusion chromatography. The structures of the isolated oligomers were revealed by single-crystal X-ray and (1)H NMR analyses. Both in solution and in crystal, the in-chain fluorene moieties stacked on top of each other, while the terminal conformation varied depending on the terminal group. These conformational characteristics were supported by molecular mechanics and dynamics calculations. The oligomers and polymers indicated hypochromism and red shift in UV absorption spectra and exclusive excimer emission in fluorescence spectra. In addition, reduced oxidation potentials were observed for the oligomers in electrochemical analyses, which suggests charge delocalization over the pi-stacked electron systems. The photophysical and electrochemical effects increased with the chain length of the oligomers and leveled off around the chain length of an oligomer consisting of five fluorene units.     

螺二芴富勒烯吡咯烷衍生物的合成及电化学和光限幅性能

设计合成了3种新颖的螺二芴键联富勒烯(C₆₀/C₇₀)吡咯烷衍生物, 其结构通过IR, ¹H NMR, ¹³C NMR和MALDI-TOF进行确证, 其电化学性质用循环伏安法进行研究. 结果表明, C₇₀衍生物6的还原电位较C₆₀衍生物7分别向负电势移动0.1, 0.12和0.01 V. 同时, 使用纳秒和飞秒激光分别研究了化合物6, 7和8的光限幅性能, 其光限幅阈值分别为15.3, 23.3和13.7 J/cm², 表明材料具有优异的光限幅性能.     

Synthesis of isomeric coumarin-fluorene hybrids by photocyclization and the photophysical features

We prepared isomeric compounds 2a and 2b having fused skeletons of coumarin and fluorene by photochemical cyclization of olefin 1. They were successfully separated by chromatography, and characterized by NMR spectroscopic and X-ray crystallographic analyses. The molecular structure of 2a was nonplanar due to the repulsion between the carbonyl group of the coumarin moiety and the methylene group at 9-position on the fluorene skeleton whilst that of 2b was planar. They showed different absorption and fluorescence features in solution whereas their spectral profiles of triplet–triplet absorption and phosphorescence were similar to each other.     

氧化偶联共聚合制备主链含β-萘烷基醚的红色发光聚合物

用氧化偶联聚合法合成了主链上含β-萘烷基醚和吡啶、二烷基芴、二苯乙烯和均四甲苯的聚合物.用FT-IR和1H NMR表征了聚合物的结构.广角X射线衍射表明共聚物的结构都是非晶态的.用UV-V is表征了共聚物的吸收特征.聚合物的荧光光谱表明,含有β-萘烷基醚和吡啶的聚合物在溶液中表现为红光发射材料.含有β-萘甲醚和二苯乙烯的共聚物为黄橙光发射,通过改变单体含量也可实现红光发射.含有β-萘甲醚和二烷基芴的聚合物固体有望成为白光发射材料.     

Synthesis,structure, and evaluation of the effect of multiple stacking on the electron-donor properties of pi-stacked polyfluorenes

A versatile synthesis of pi-stacked polyfluorenes is described. These polyfluorenes retain their cofacial conformations both in solution and in the solid state as was judged by NMR spectroscopy and X-ray crystallography. The experimental electron-detachment energies of F1-F4 showed linear correlations with the quantity 1/n, where n is the number of fluorene moieties. These correlations allowed the estimation of the vertical ionization potential (IP) of 7.10 eV and the oxidation potential (Eox) of 0.97 V versus SCE for the multiply stacked polyfluorene donor with an infinite number of fluorene moieties. These observations with pi-stacked polyfluorenes may prove to be highly relevant to the electron-transport phenomenon observed in DNA through pi-stacked bases.