物理化学学报 >> 1999, Vol. 15 >> Issue (09): 805-811.doi: 10.3866/PKU.WHXB19990907

研究论文 上一篇    下一篇

固态类杂芪分子一阶超极化率测定及溶剂效应

詹传郎, 王夺元   

  1. 中国科学院化学研究所分子中心,光化学开放实验室,北京 100101
  • 收稿日期:1998-11-20 修回日期:1999-03-22 发布日期:1999-09-15
  • 通讯作者: 王夺元

Determination of the Molecular First-order Hyperpolarizabilities of Six Stilbzolium-like Dyes in Solid State and the Solvent Effects

Zhan Chuan-Lang, Wang Duo-Yuan   

  1. Laboratory of Photochemistry,The Center for Molecule Science,The Chinese Academy of Sciences,Beijing 100101
  • Received:1998-11-20 Revised:1999-03-22 Published:1999-09-15
  • Contact: Wang Duo-Yuan

摘要:

用溶致变色法研究溶剂对反式-(4-N ,N 二甲氨基 )-(4-N-甲基吡啶基 )杂芪碘 (DAPSI) ,反式-(2-N-甲基吡咯基 )-(4-N-甲基吡啶基 )杂芪碘 (MPPSI) ,反式-(2-吡咯基 )-(4-N-甲基吡啶基 )杂芪碘 (PPSI)、反式-(2-呋喃基 )-(4-N-甲基吡啶基 )杂芪碘 (FPSI)、反式-(2-噻吩基 )-(4-N-甲基吡啶基 )杂芪碘 (TPSI)和反式-(4-N-甲基吡啶基 )杂芪碘 (PSI)的分子一阶超极化率 (βxxx)的影响 ,揭示了溶剂极性 (ET(30 ) )与类杂芪染料的 βxxx值间很好的线性关系和影响规律 ,引入了溶剂化效应对待测化合物分子能级的影响与待测化合物分子间相互作用能级间存在等效能级的概念 ,从溶剂极性 (ET(30 )值 )与 βxxx值间的线性关系求出了在纯固态下类杂芪染料的 βxxxs值 ,及基态与第一激发态间跃迁能和最大吸收波长 .证明了MPPSI、PPSI、FPSI、TPSI和PSI在纯固态下的 βxxxs值与给电子取代基的富电子性间有很好的线性关系.

关键词: 类杂芪染料, 吡啶碘盐, 溶剂效应, 溶致变色, 分子-阶超极化率

Abstract:

By using the solvatochromism, we have studied the solvent effects on the molecular first-order hyperpolarizabilities of six stilbazolium like dyes: trans-4-(N,N-dimethylamino)-(4-N-methylpyridinio)-stilbazolium iodide (DAPSI),trans-(N-methylpyrrol-2-yl)-4-(N-methyl-pyridinio)-stilbazolium iodide(MPPSI),trans-(pyrrol-2-yl)-4-(N-methyl-pyridinio)-stilbazolium iodide(PPSI),trans-(furan-2-yl)-4-(N-methyl-pyridinio)-stilbazolium iodide (FPSI) and trans-(thiophene-2-yl)-4-(N-methyl-pyridinio)-stilbazolium iodide (TPSI),and trans-(4-methyl-pyridinio)-stilbazolium iodide(pSI),and obtained the results that the molecular hyperpolarizabilities are in linear correlation with the solvent polarity, E T(30),and introduced the concept that the effects on the energy levels of the compound by the solvent is equavalent to those by the surrounding molecules of the compound itself ,from which we calculated the molecular first order hyperpolarizabilities β s xxx of the six dyes in pure solid state, as -46,7,-7 1,-6 7,-3 1,-2 2,and 0 55×10 -27 esu for DAPSI, MPPSI, PPSI, FPSI, TPSI and PSI, respectively. And we also obtained the perfect linearity relationship between the β s xxx and the electron excessivities of the donor for the latter five dyes.

Key words: Stibazolium-like, Dye, Pyridium, Solvent effect, Hyperpolarizability, Solvatochromism