Belding Lee, Guest Matt, Le Sueur Richard, Dudding Travis
Brock University , 1812 Sir Isaac Brock Way , St. Catharines , Ontario L2S 3A1 , Canada.
J Org Chem. 2018 Jun 15;83(12):6489-6497. doi: 10.1021/acs.joc.8b00770. Epub 2018 May 31.
The synthesis of cyclopropenium-substituted amino compounds and analysis of their photophysical properties is described. Systematic structural modifications of these derivatives lead to measurable and predictable changes in molar extinction coefficients, quantum yields, and Stokes shifts. Using time-dependent density functional theory (TD-DFT) calculations, the origin of these trends was traced to internal charge transfer (ICT) coupled with ensuing structural reorganization for select naphthalene functionalized derivatives. Associated with this structural reorganization was an inward gearing of the cyclopropenium ring and twisting of the peri-NMe group into coplanarity with the naphthalene ring system. Further, reinforcement of an intramolecular H-bond (IMHB) in the excited state of these derivatives alludes to the importance of photoinduced H-bonding in this new class of cyclopropenium based fluorophores.
本文描述了环丙烯基取代氨基化合物的合成及其光物理性质分析。对这些衍生物进行系统的结构修饰会导致摩尔消光系数、量子产率和斯托克斯位移发生可测量且可预测的变化。通过含时密度泛函理论（TD-DFT）计算，这些趋势的起源可追溯到内部电荷转移（ICT）以及随后选定的萘官能化衍生物的结构重组。与这种结构重组相关的是环丙烯基环的向内啮合以及邻位-NMe基团扭曲成与萘环系统共面。此外，这些衍生物激发态下分子内氢键（IMHB）的增强暗示了光诱导氢键在这类新型环丙烯基荧光团中的重要性。
