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合成了以荧光素为光敏剂的电子给体-受体二元化合物荧光素蒽醌甲酯(FL-AQ),用吸收光谱、荧光光谱、荧光寿命研究了该化合物在乙醇溶液中的光物理性质,并首次用纳秒级瞬态吸收光谱检测了此化合物分子内光诱导电子转移所形成的电荷分离态.在溶液中激发FL,电子可从FL有效地转移到AQ,其速率常数为3.95×109s-1,效率为95%.但由于电荷分离态寿命较短,瞬态吸收信号弱,若在此溶液中加入二氧化钛(TiO2)纳米胶体,使FL-AQ吸附在胶体上,电荷分离态信号明显增强.480nm处FL+·的寿命为11.1μs;560nm处AQ-·的寿命为8.93μs. 相似文献
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合成了以-(CH_2)_4连接的荧光素、紫精、咔唑二元及三元化合物,运用吸收光谱,荧光光谱及荧光寿命研究了荧光素-咔唑、紫精-荧光素、紫精-荧光素-咔唑等二元、三元化合物分子内的光致相互作用,结果表明:分子内紫精对荧光素荧光的淬灭主要通过形成不发荧光的络合物,荧光淬灭的效率φ_Q为0.97,荧光寿命淬灭的效率φ_(ET)为0,不发荧光络合物的淬灭的效率φ_C为0.97.咔唑对荧光素荧光的淬灭则以动态的光致电子转移过程为主,荧光淬灭的效率φ_Q为0.63,荧光寿命淬灭的效率φ_(ET)也为0.63,不发荧光络合物的淬灭效率φ_C为0.在三元化合物内紫精-荧光素和荧光素-咔唑对光致相互作用是一种竞争过程,以荧光素-咔唑对间的动态电子转移反应为主,φ_Q为0.97,φ_(ET)为0.65,不发荧光络合物的淬灭效率φ_C为0.32.从反应自由能变化的角度对此进行了讨论. 相似文献
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The photocycloadditions between 8-methoxypsoralen(8-MOP) and olefines have been in-vestigated. It gives a series of head-to-tail cycloadducts. From the reaction rates and cal-culated values of polarizability of olefines it indicates that reaction rates are dependent onthe polarizability of olefines. The stereochemistry of these products has been studied. Inview of these results it shows that the electron-deficient C_3-position of the triplet state of 8-MOP attacks the olefines electro-philically at first, then the reactions proceed to form pro-ducts via diradical mechanism. 相似文献
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合成了以共价键相连的荧光素-卟啉二元分子.研究了荧光素酯与卟啉分子间和分子内的能量及电子转移过程.分子间的荧光猝灭实验表明,当激发荧光素时,荧光素的单重态能量有效地传给卟啉,动态荧光猝灭速度常数(k_d)为1.3×10~(12)s~(-1)·mol~(-1)L.吸收光谱和NMR谱结果表明荧光素与卟啉间有基态相互作用,其静态荧光猝灭速度常数(k_s)为3.6×10~(12)s~(-1)·mol~(-1)·L.在二元分子中,当激发荧光素时,从荧光素到卟啉的单重态能量传递效率在0.90以上,速度常数为 1.2×10~(10)S~(-1)·mol~(-1)·L,溶剂极性对其影响不大.当激发卟啉时,在极性溶剂中发生了电子转移,其转移效率为0.51,速度常数为2.3×10~8s~(-1)·mol~(-1)·L. 相似文献
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A series of polyads consisting of covalently-(CH2)4-linked fluorescein with carbazole and violger.Live been synthesized and characterized The studies of absorption,emission spectra and fluorescence lifetime quenching indicated that the intramolecular fluorescence quenching of fluorescein by violgen is mainly a static process through the formation of non emission complex (fluorescence quenching efficiency φQ=0.97,lifetime quenching efficiency φH 0,quenching efficiency of formation of non-emission complex φC=0.97); while the quenching by carbazole is mainly a dynamic electron transfer process (φQ=0.63,φET=0.63,φC=0).In the violgen-fluorescein-carbazole triads,φQ=0.97,Q ET=0.65,φC=0.32,which suggests that the photoinduced interaction of fluorescein-carbazole pair and that of violgen-fluorescein pair are in a competitive process,the dynamic electron transfer from carbazole to fluorecein is dominant in the process The free energy change of the photoinduced electron transfer and the back reac-tiorns i 相似文献
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功能性多吡啶配体的合成 总被引:13,自引:0,他引:13
经过多步反应,合成了10个新的多吡啶配体,其中,有带强吸附性的基团(磷酸基、羧基),有对pH敏感及具有平面大共轭体系的联多吡啶配体及其中间体,用光谱鉴定了它们的结构. 相似文献
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