两种萘酰亚胺类化合物及其聚合物荧光性质的研究

本文以1,8萘酰亚胺为原料,合成了两种萘酰亚胺类型的化合物,系统地研究了它们在不同溶剂中的吸收光谱和荧光光谱.并以这两种化合物单体为基础,通过共聚合成了它们与甲基丙烯酸甲酯和N 乙烯基咔唑的嵌段共聚物.研究了聚合物在溶液和薄膜中的荧光性质.研究结果证明,所得共聚物不但保持了单体的基本荧光特性,其溶解性、成膜性、热稳定性等都得到了大大改善,是一种有应用前景的有机发光半导体材料.此外,本文还利用荧光猝灭的手段研究了萘酰亚胺类化合物与C₆₀之间的相互作用.     

蓝光萘酰亚胺发光材料的合成与表征

通过在4位引入不同芳香基团,采用Suzuki和Stille偶联反应,设计与合成了一系列新型1,8-萘酰亚胺类荧光染料,并研究了它们的紫外-可见吸收、荧光发射和电化学行为等光物理性质。这些化合物在甲苯中均发射蓝色荧光,最大吸收和荧光发射峰分别在357～378和423～451nm之间,且随着芳香基团供电性增强,吸收和荧光发射波长发生红移。芳香基团的结构对化合物的发光效率影响很大,其中,取代基为甲氧基苯的化合物具有最高的荧光量子效率,可达0.98,而取代基为噻吩的化合物荧光量子效率最低,只有0.17。电化学循环伏安研究表明该类化合物具有较高的电子亲合力,不同芳香基团的引入只影响化合物的被占分子轨道(HOMO)能级,而对化合物的最低空分子轨道(LUMO)能级没有影响,即LUMO能级由1,8-萘酰亚胺单元决定。     

新型三嗪桥连的双1,8-萘酰亚胺衍生物的合成及其光物理行为

以1,8-萘酰亚胺和三聚氯氰为主要原料, 合成了两种由三嗪环桥连的双1,8-萘酰亚胺化合物3 和5. 采用紫外-可见光谱和荧光光谱等手段考察了两种化合物在不同溶剂中的光物理行为. 与参比化合物N-丁基-1,8-萘酰亚胺相比, 在二氯甲烷、三氯甲烷和甲醇等极性溶剂中, 化合物3和5除了在短波区(λ<400 nm)存在1,8-萘酰亚胺的特征荧光发射峰外, 在长波区(>450 nm)均产生一个较强的新荧光发射峰, 表现出分子内激基缔合物的光物理行为. 与化合物5相比, 由于化合物3特殊的构象异构, 其荧光强度发生严重的猝灭. 在非极性溶剂甲基环己烷中, 化合物5 由于存在较强的分子间氢键作用而聚集, 受激后形成了较稳定的分子间激基缔合物, 但未观察到明显的分子内激基缔合物的形成. 在甲苯溶剂中, 化合物3和5与甲苯分子形成了激基复合物, 并未形成分子内激基缔合物. 进一步研究3和5的固态激发态性质, 发现化合物3和5的固体薄膜受激后分别在465和469 nm处出现激基缔合物的特征荧光发射峰.     

含3,5-二甲基二氮杂萘酮联苯结构聚醚酰亚胺的合成与性能

由4-[(3,5-二甲基-4-羟基)苯基]-2,3-杂萘-1-酮与4-氯-N-苯基邻苯酰亚胺通过亲核取代反应、水解反应和脱水反应合成了一种新型不对称含二氮杂萘联苯结构的二酐单体,并对其进行结构表征.由新型二酐单体与市售的二胺单体通过“一步法”溶液聚合反应合成了5种含二氮杂萘酮联苯结构的聚醚酰亚胺.通过FTIR和¹HNMR方法研究了聚合物的结构及性能.结果表明,该类聚合物既具有较高的耐热性能,又可以在室温下溶解于非质子极性溶剂,如N-甲基吡咯烷酮和间甲酚等.     

荧光聚合物研究进展

本文总结了近年来荧光聚合物的研究进展,主要介绍了荧光聚合物的分类：按其溶解性能可分为非水溶性、水溶性和两亲荧光聚合物三大类;荧光聚合物的合成：荧光化合物为引发剂、荧光化合物为链转移剂、荧光功能单体聚合、荧光化合物与聚合物的化学键合、非荧光功能单体聚合等五种制备荧光聚合物的设计合成方法;荧光聚合物的应用：荧光聚合物在荧光化学传感器、荧光分子温度计、荧光造影、药物载体、荧光探针等方面的应用研究。     

水溶性1，8-萘酰亚胺衍生物的合成及其对有机溶剂中少量水的识别

萘二甲酸酐与2-(2-氨乙基氨基)乙醇在乙醇中反应合成了一种新型水溶性1,8-萘酰亚胺衍生物--N-[2-(2-羟乙基氨基)-乙基]-1,8-萘酰亚胺(3),其结构经1H NMR,IR,MS和元素分析表征.荧光光谱分析发现3在不同溶剂中具有不同的荧光性质,在非(或弱)极性-非质子性溶剂、极性-非质子溶剂中几乎不产生或产生较弱的荧光,而在极性-质子性溶剂中产生较强的荧光,在水中的荧光最强.这种特性使3有望用于识别有机溶剂中的少量水.     

Synthesis and Spectra Analyses of Eu（lll） Binary Complexes with Polycarboxylic Acid

分别以1,3,5-苯三甲酸（H3BTC）、苯六甲酸（H6MTA）和1,2,3,4,5,6-环己六甲酸（H6CCA）为配体合成了Eu（Ⅲ）的二元发光配合物Eu（BTC）2H2O,Eu2（MTA）4H2O和Eu2（CCA）4H2O.通过元素分析、红外光谱和等离子体原子发射光谱对其化学组成进行了结构表征,表征结果与理论吻合良好.利用荧光分度计,研究了所制备配合物室温条件下的荧光性能（荧光激发光谱、发射光谱、荧光寿命和量子效率）,结果表明：该三种配合物在紫外光照射下,均发射Eu（Ⅲ）离子的特征红光,其中Eu2（MTA）4H2O（量子效率=10.25%,荧光寿命=0.36 ms）的荧光性能最好,这说明配体H6MTA的能级与Eu3＋离子能级匹配程度很好.另外,通过热分析对配合物的热稳定性进行了分析,结果表明：该三种配合物均具有良好的热稳定性,主要分解温度远高于其他β-二酮配合物.     

N-Cycl[3,2,2]azine甲酰脲衍生物的合成及其荧光性质研究

设计合成了N-Cycl[3,2,2]azine甲酰脲衍生物6,通过X-Ray对其进行了结构表征.研究了其在不同溶剂中的紫外光谱和荧光光谱,比较了它们的荧光量子效率.发现在乙腈中,其相对荧光量子产率达0.68.该化合物对溶剂极性也有一定的敏感性.上述研究结果为进一步选择其它客体,探索化合物6在分子识别中的应用建立了基础.     

有机锡缩聚物荧光染料的合成及结构表征

有机锡缩聚物荧光染料是近几年开始研究的、具有广泛应用前景的高分子材料。本文用界面缩聚法,将二烷基二氯化锡与几种染料单体反应合成了一系列有机锡缩聚物荧光染料。探讨了聚合条件,例如两相单体浓度比,搅拌反应时间、pH值等对聚合反应产率的影响。测定了聚合物的溶解性质,并用红外光谱法对聚合物进行了结构表征和测定了染料的热稳定性。     

聚萘的合成及其光电器件*

本文系统回顾和总结了化学方法制备聚萘的历史进程和研究成果, 包括上世纪六十年代的Lewis酸直接氧化萘单体缩聚法和最近的萘衍生物的Yamamoto法和Suzuki法。指出萘基格氏试剂中介法是高产率获得各种具有确定结构聚萘的有效方法;等离子体沉积法等可直接制备聚萘膜,从而避免了因聚萘的难溶、难熔而引起的加工成型问题;而Yamamoto法和Suzuki法则是合成可溶性聚萘衍生物的有效途径,且聚合物产物具有优异的荧光性能,荧光量子效率最高达0.96。对于萘在1,4- 和5,8-位同时链接形成的规整的一维石墨结构具有非常高的菲边缘碳和边缘碳密度,有望显示出比二维石墨材料更高的锂掺杂能力,另外其较强的蓝色荧光发射特性以及高温稳定性,聚萘在锂离子二次电池电极材料、聚合物发光二极管、耐高温材料等领域都将显示出诱人的应用前景。     

Liquid-crystalline properties of chiral malolactonate monomers and their comb-shaped polymers

A series of optically pure mesogenic ester precursors, and the malolactonate monomers containing mesogenic alcohols obtained from them were prepared and polymerized to homopolymers and copolymers. The liquid-crystalline properties of the precursors, monomers and polymers were investigated by differential scanning calorimetry, polarized light microscopy and wide angle X-ray diffraction. The liquid-crystalline properties of the chiral mesogenic precursors and monomers were only slightly influenced by the chemical structure, configuration and the alkyl spacer length of the mesogenic alcohol substituent of the ester. The precursor, 1-[6-(4'-hexyloxy-4-biphenylyl)oxyhexyl] hydrogen (S)-O-mesylmalate (V-(S)-6) formed smectic E and smectic A phases on melting, while the monomer, 6-(4'-hexyloxy-4-biphenylyl)oxyhexyl (R)-malolactonate (II-(R)-6) showed only a crystal-isotropic phase transition. In contrast, the homopolymer of the latter exhibited a chiral smectic C phase. Copolymers from 2-(4'-hexyloxy-4-biphenylyl)oxyethyl (R)-malolactonate (II-(R)-2) also formed chiral smectic C phases.     

Preparation and polymerization of thyroxine methacrylate monomers

Thyroxine methyl ester amides of mono-, di-, and tri-glycyl methacrylates have been prepared. Water-soluble polymers formed from thyroxine methacrylate monomers by free-radical copolymerization with acrylamide had molecular weights of (2–4) × 10⁴ (by viscometry). A fluorescent polymer was prepared by copolymerization with a fluorescein methacrylate monomer. Similarly, a polymeric thyroxine material was prepared with amine functionality by copolymerization with N-3-aminopropylmethacrylamide. These polymers may have interesting biological and immunochemical properties.     

Copolymerization of vinyl monomers with irradiated acrylamide crystals

Liquid vinyl monomers (styrene and methyl methacrylate) were copolymerized with γ-irradiated acrylamide in a two-phase system. The products obtained were mainly diblock copolymers of acrylamide and the vinyl monomer used, but small amounts of homopolymers were also formed. The effects of radiation dose, copolymerization temperature, initial molar ratio of monomers, crystal size of acrylamide, mode of irradiation, and the existence of a solvent were investigated. In addition to the conventional methods, the reaction was studied by electron spin resonance spectroscopy. A mechanism was proposed and a kinetic rate equation was established for this copolymerization. Characterization of the copolymers was made by physical and mechanical testing.     

Hybrid copolymerization of cyclic and vinyl monomers

In this work,we report the hybrid copolymerization of various cyclic monomers and vinyl monomers.Our studies demonstrate that 1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino) phophoranyliden-amino]-2 5,5-catenadi(phosphazene) (t-BuP 4) can catalyze the hybrid copolymerization of caprolactone (CL),lactide (LA) or cyclic carbonate ester with acrylate or methyl acrylate.However,the polymerization of cyclosiloxane with vinyl monomers yields two corresponding homopolymers,and the polymerization of lactone with acrylonitrile (AN) produces only polyacrylonitrile.Clearly,the extent of matching of activity between a monomer and an active center determines whether or not there is hybrid copolymerization.     

New fluorescent monomers and polymers displaying an intramolecular proton‐transfer mechanism in the electronically excited state (ESIPT), 1. Synthesis of benzazolylvinylene derivatives and its copolymerization with methyl methacrylate (MMA)

Six new fluorescent monomers of the benzazole family were synthesized by the reaction of 2‐(5′‐amino‐2′‐hydroxyphenyl)benzazole derivatives and differently functionalized vinylene compounds. The radical copolymerization of the monomers with MMA results in transparent and fluorescent polymers with good optical and thermal properties. These monomers and copolymers emit fluorescence with a large Stokes shift due to the intramolecular proton‐transfer mechanism in the electronically excited state (ESIPT).     

Backbone modifications of aromatic peptide nucleic acid (APNA ) monomers and their hybridization properties with DNA and RNA

Aromatic peptide nucleic acid (APNA) monomers containing N-(2-aminobenzyl)-glycine, N-(2-aminobenzyl)-(R)- or -(S)-alanine, and N-(2-aminobenzyl)-beta-alanine moieties as part of their backbone were synthesized. These novel analogues were incorporated as a single "point mutation" in PNA hexamers, and their physicochemical properties were investigated by UV thermal denaturation and CD experiments. Destabilization in triplex formation between the PNA-APNA chimeras and complementary DNA or RNA oligomers was observed, as compared to the PNA control. The APNA monomer composed of the N-(2-aminobenzyl)-glycine backbone led to the smallest decrease in the thermal stability of the triplexes formed with DNA and RNA, while maintaining selectivity for base-pairing recognition. Since the PNA-APNA chimeras are more lipophilic than the corresponding PNA homopolymers, these oligomers may also exhibit better cell membrane permeability properties.     

The cationic polymerization and copolymerization of isopropenylmetallocene monomers

Three types of isopropenylmetallocene monomers were synthesized and subjected to polymerization and copolymerization by cationic initiators; (1) isopropenylferrocene (IF); (2) (η⁵-isopropenylcyclopentadienyl)dicarbonylnitrosylmolybdenum (IDM); and (3) 1,1′-diisopropenylcyclopentadienylstannocene (DIS), and related derivatives of each. IF was synthesized by a three-step procedure involving the acetylation of ferrocene, conversion of the latter to 2-ferrocenyl-2-propanol, and dehydration of the carbinol. IF was homopolymerized under various cationic initiation conditions, but only low molecular weight homopolymers were obtained. Copolymerization of IF with styrene and with p-methoxy-α-methylstyrene also gave only low molecular weight products. The formation of only low molecular weight polymers in all polymerization reactions is believed to result from the effect of the unusually high stability of ferrocenyl carbenium ions on its propagation reaction. The observed polymerization behavior of α-trifluoromethylvinylferrocene is in accord with this conclusion. IDM and DIS did not form polymeric products under cationic conditions, although copolymers could be obtained for each of these monomers and styrene with a free radical polymerization initiator (AIBN).     

Fluorescence spectra and structure of the difluoro(dibenzoylmethanato)boron monomers and dimers absorbed on silica gel

It has been shown that difluoro(dibenzoylmethanato)boron ((dbm)BF₂) can be absorbed on silica gel in the form of fluorescent monomers and dimers with the emission properties that change in the presence of vapors of volatile organic compounds, such as ethanol, acetone, toluene, and meta-xylene. Fluorescence quenching was observed for the (dbm)BF₂ monomers and dimers in the case of ethanol and acetone, whereas the formation of fluorescent exciplexes with monomers and enhancement of the dimer fluorescence were observed in the case of toluene and meta-xylene. Results of the quantum-chemical calculations of the structure of the (dbm)BF₂ monomer complex with the matrix and toluene and (dbm)BF₂ dimers with matrix are presented.     

Polymerization of methyl 12-acryloxystearate,N,N-dimethyl 12-acryloxystearamide,and methyl 14-acryloxyeicosanoate

Several homopolymers and copolymers of the title compounds have been prepared by radical initiation with potassium persulfate or diethyl azobisisobutyrate. The copolymers exhibit a combination of the properties of the homopolymers of the monomers. The homopolymers are adhesive, very slightly elastic, and show cold flow. Several of the copolymers show possible promise for use as adhesives.     

Side-chain crystallinity. V. Heats of fusion and melting temperatures on monomers whose homopolymers have long side chains

Heats of fusion and melting temperatures were obtained for selected monomeric n-alkyl acrylates, N-n-alkylacrylamides, and vinyl esters. The corresponding thermodynamic parameters for homopolymers, derived from these monomers, had been reported previously from this laboratory. The α-hexagonal crystal modification was indicated near the melting point for the higher n-alkyl acrylates, but a β form was stable at low temperatures for the entire series. The magnitude of the heats of fusion indicated β polymorphs for vinyl esters in support of x-ray diffraction analysis from the literature. Because hexagonal crystal geometry prevailed in all reported homopolymers having long side chains, greater emphasis was placed on thermodynamic data for monomers exhibiting this crystal modification. Accordingly, a convergence temperature was estimated statistically for the α-hexagonal crystal modification of these systems and appropriate literature values of the n-alkanes and ethyl esters. The convergence temperature was computed to be 135°C, uncorrected for the entropy of disorientation. The anomalously large interfacial end-packing-defect energy of the poly(n-alkyl acrylates) and the poly-N-n-alkylacrylamides was shown to be associated with a high energy barrier to molecular transport in the melt as the vitreous state was approached. In support of this conclusion, similarity of the glass and melting transition temperatures of these homopolymer homologs occurred near their critical side-chain lengths, below which the homopolymers are amorphous. A special critical requirement of nucleus length was not indicated from rough estimations of nucleation parameters for the poly(n-alkyl acrylates). These findings lent increased, but still not unqualified, support to an x-ray diffraction study from the literature. The latter had specified the inclusion of the entire side chain and the main-chain units in the crystal lattices of the higher poly(n-alkyl acrylates).