光谱学分析-chapter04-荧光-03-CTC.ppt

分子内的跨环共轭和/或跨环电荷转移 Transannular conjugation or Transannular charge transfer[UV-Vis, p258-] Transannular：across a ring, or between different parts of a ring 4.2 电荷转移荧光：两种机理 D* A + D+A- hv + DA A* D + A-D+ A D hv + 电荷转移跃迁应用举例: 药物分析 氯冉酸-quinolines；7,7,8,8-四氰基对苯醌；四氰乙烯 高温 极性溶剂 低温， 非极性或弱极性溶剂 4.3. 分子内和扭转的分子内电荷转移荧光 intramolecular and twisted intramolecular charge transfe, ICT/TICT Photophysical and Photochemical Switches Based on Twisted Intramolecular Charge Transfer (TICT) States. W. Rettig. Appl. Phys. B 45, 145 149 (1988) In systems like DMABN which are flexible but planar in the ground state, the formation of the TICT state involves intramolecular twisting in the excited state which can be viewed as an adiabatic photoreaction proceeding on the $1 hypersurface [-4] (Fig. 1). The originally reached locally excited LE state with planar conformation has only partial CT character (large mesomeric interaction between D and A results in uncomplete charge separation) whereas in the twisted TICT conformation, either a full or no electronic charge is transferred from D to A, at least in the simple n model, because the mesomeric interaction between D and A is blocked. LE: amino-group is not part of the delocalized electron system. 氨基不是离域电子体系的一部分。 ICT/TICT: amino-group twists to allow the nitrogen electrons to be in conjugation with the naphthalene ring.氨基扭转以允许氮电子处于与萘环共轭的状态。 S0, nonpolar LG, Locally ground state S1, nonpolar S1, ct ET hnF,ct hnF,np hnA If the solvent is nonpolar, the LE state is the low-energy state and emitting species. In more polar solvent, the charge transfer state becomes the low- energy state and emits at longer wavelengths. Intramolecular Donor-Acceptor Systems. 10. Multiple Fluorescences from 8-( Phenylamino) 1 –naphthalenesulfonates. Edward M. Kosower and Hannah Kanety. J . Am. Chem. Soc. 1983, 105, 6236-6243. 理论：在分子处于激发态时，因光诱导的电荷转移使分子强烈极化，再由溶剂的作用使分子内给体部分与受体部分间发生了“完全”的电荷转移，与此同时，分子上述两部分间发生扭转，使原来的共平面结构破坏，实现所谓的自去耦(self decoupling)效应。这种扭