Effect of Terminal Fluorination on Chiroptical Properties of Carbo[5-8]helicenes: A Systematic Computational Study at the RI-ADC(2) Level.

Abstract

In this article, effects of di-, tetra-, and octafluorination on the structural and chiroptical properties of carbo[5-8]helicenes are reported. Three fluorinated derivatives are designed from each parent carbohelicene by substituting either one, two, or four hydrogens at each terminal ring with fluorine atoms. Excited states properties such as UV-vis and CD spectra of all the six fluorinated carbohelicenes are computed at the ADC(2)/def2-TZVP level, and the results are compared against the results of their respective parent carbohelicene. In addition, CPL properties are also computed at the same level of theory. In the case of carbo[5]helicene (5H), gCPL decreases with an increase in the degree of fluorination. A similar observation is made in carbo[6]helicene (6H) too, although the value for tetrafluorinated 6H is slightly larger than for difluorinated 6H. Di- and tetrafluorination in carbo[7]helicene (7H), and all types of considered fluorination in carbo[8]helicene (8H) produce improved gCPL results. Results for fluorescence rate constants are also shown. Results are analyzed in terms of the transition dipole moment vectors and the angles between those.