新型有机类杂芪染料的合成及其光物理性质研究

THE SYNTHESIS OF THE STILBAZOLIUM-LIKE DYES AND THEIR PROPERTIES OF THE LOWEST EXCITED SINGLET STATE

利用改进的碱缩合或酸催化反应 ,合成了 8种类杂芪染料 :反式 ( 2 N 甲基吡咯基 ) ( 4 N 甲基吡啶基 )杂芪碘 (反式 MPPSI)、反式 ( 2 吡咯基 ) ( 4 N 甲基吡啶基 )杂芪碘 (反式 PPSI)、反式 ( 2 呋喃基 ) ( 4 N 甲基吡啶基 )杂芪碘 (反式 FPSI)、反式 ( 2 噻吩基 ) ( 4 N 甲基吡啶基 )杂芪碘 (反式 TPSI)、反式 ( 4 N 甲基吡啶基 )杂芪碘 (反式 PSI)、反式 ( 4 甲基 ) 4( 4 N 甲基吡啶基 )杂芪碘 (反式 MPSI)、反式 ( 4 胺基 ) ( 4 N 甲基吡啶基 )杂芪碘 (反式 APSI)和反式 ( 4 N ,N 二甲胺基 ) ( 4 N 甲基吡啶基 )杂芪碘 (反式 DAPSI)其中PPSI、FPSI和TPSI为首次报道的新型染料 .研究了这 8种染料的基本光物理性质 .应用线性Ham mett方程 ,得到了类杂芪染料的电荷转移性质、荧光最大发射波数及Stock’s位移和Hammett常数σ或五员杂环的富电子性ρ(C) D 间的线性相关性 ,由于类杂芪染料分子的最低跃迁能 (υa)可与σ或ρ(C) D 线性相关 ,所以类杂芪染料的电转移态性质、荧光最大发射波数及Stock’s位移也可与υa 线性相关 ,从而得到了拓展的线性Hammett方程 .

Eight stilbazolium-like dyes in which trans-(4-N, N-dimethylamino)-(4-N-methylpyridinio)-stilbazolium Iodide(trans-DAPSI), trans-(4-amino)-(4-N-methylpyridinio)-stilbazolium Iodide (trans-APSI), trans-(4-methyl)-(4-N-methyl pyridinio)-stilbazolium Iodide (trans-MPSI), trans-(4-N-methylpyridinio)-stilbazolium Iodide (trans-PSI) and trans-(N-methylpyrrol-2-yl)-4-(N-methyl-pyridinio)-stilbazolium Iodide (trans-MPPSI) are known and trans-(pyrrol-2-yl)-4-(N-methyl-pyridinio)-stilbazolium Iodide (trans-PPSI), trans-(furan-2-yl)-4-(N-methyl-pyridinio)-stilbazolium Iodide (trans-FPSI) and trans-(thiophene-2-yl)-4-(n-methyl-pyridinio)-stilbazolium Iodide (trans-TPSI) are the first reported new compounds, were prepared by basic condensation and acidic catalysis. We found that the Spectroscopic Hammett Equation is valid not only for the benzene derivatives, for examples DAPSI, APSI, MPSI and PSI, but also for the five-member-heterocyclic derivatives, for examples, MPPSI, PPSI, FPSI, TPSI and PSI, in which the Hammett constant σ is replaced with the electron excessivity ρ(C)_D. Furthermore, the similar linear correlation can be also extended for the properties of the charge transfer state. From the above two types of correlation, we can deduce that the linear correlation between the transition energy υ_a from the ground to the lowest excited singlet states and the properties of the charge transfer state of the dyes. For the fluorescence emission maximum wavenumber (υ_F) or the conrresponding Stock's shifts, we can also obtain the similar linear correlation as Spectroscopic Hammett Equation.\;