时间分辨荧光光谱研究聚2-乙烯基萘与对苯二甲酸二甲酯形成的三分子激基复合物

本文研究了在稀溶液中,聚2-乙烯基萘分子内不同生色团之间相互作用后先形成分子内激基缔合物,然后与受体分子相互作用后再生成三分子激基复合物的机理。测定了聚2-乙烯基萘分子内激基缔合物的荧光寿命的r_2=18.83ns;形成三分子激基复合物的速度常数k_7=4.18×10~9(mol/L)~(-1)S~(-1),受扩散速度反应控制。首次提出了激基缔合物或激基复合物可能是形成三分子激基复合物的中间体,并提出了由激基缔合物再形成三分子激基复合物的光物理过程的理论模型。     

STEADY-STATE AND TIME-RESOLVED FLUORESCENCE STUDY OF TRIPLE EXCIPLEX IN THE SYSTEM OF POLYACENAPHTHALENE AND TEREPHTHALIC DIMETHYLESTER

Triple exciplex formed between polyacenaphthalene and terephthalic dimethylester (TDE) has been studied by means of the steady-state and time-resolved fluorescence spectra. The theoretical model of the triple exciplex formation for a flexible polymer chain in a dilute solution has been proposed. The fluorescence decays of the monomer, the exciplex and the triple exciplex obey a double exponential rule in the pbotophysical processes of the triple exciplex formation. The association rate constant of the exciplex formation is k_3=6.0×10~9s~(-1)(mol/L)~(-1); the association rate constant of the triple exciplex formation is k_6=5.2×10~7s~(-1). A mechanism for the triple exciplex formation from the exciplex to the triple exciplex has been proved through the noncrystal films corresponding to the same concentrations of the solution systems and the fluorescence lifetimes of the intramolecular excimer.     

N-乙烯基咔唑的光聚合

N-乙烯基咔唑的三氯甲烷溶液经光照后可以获得聚N-乙烯基咔唑,这一结论已经通过荧光光谱和NMR谱得到证实,产率很高可达70％。又通过荧光淬灭实验证实:这一反应首先在光照下形成激基复合物,由激基复合物分解产生自由基而引发N-乙烯基咔唑的聚合,此外,本文还研究了光强、N-乙烯基咔唑的浓度和光照时间对产率的影响。     

甲苯、萘、蒽与1.4-二氰基苯形成的激基复合物荧光光谱的研究

比较了甲苯、萘、蒽在与1.4-二氰基苯(DCB)形成激基复合物能力上的差别,估算了它们与DCB形成激基复合物的活化能分别为0.48、1.07、1.22kcak/mol。根据其荧光光谱、活化能和激发态分子电子云密度的分布,指出影响激基复合物形成的因素,除了电子电离能和电子亲和力外,还有激发态分子的电子云密度分布和分子的体积效应。在与DCB形成激基复合物的能力上应该是甲苯>萘>蒽。苯环与苯环相重叠可能是比较有利的互叠方式。     

TIME-RESOLVED FLUORESCENCE STUDY OF TRIPLE EXCIPLEX FORMED IN THE SYSTEM OF POLY(2-VINYL) NAPHTHALENE AND TEREPHTHALIC DIMETHYLESTER

An intramolecular excimer of poly(2- vinyl) naphthalene was formed by non-adjacentchromophores interaction, then a triple exciplex was formed by interaction with the acceptormolecule further in dilute solution. The lifetime of the intramolecular excimer of poly(2-vinyl) naphthalene, τ_2 = 18.83 ns and the rate constant for the triple exciplex formation,k_7 = 4. 18× 10~9 (mol/L)~(-1)s~(-1), under diffusion-control were measured. An excimer or anexciplex could be an intermediate of the triple exciplex formation. A theoretical model ofthe triple exciplex formation is proposed.     

丙基咔唑与蒽之间电子激发态能量传递

本文研究了以丙基咔唑为能量传递给体，蒽为受体时分子电子激发态能量传递过程，用筒化模型计算可得其传递速率为ｋＥＴ＝１。３×１０＾１０ｍｏｌ／Ｌ）＾－１Ｓ＾－１，并且测定了丙基咔唑在苯溶液中的荧光寿命τＤ＝８．３ｎｓ。