Coherent Exciton Delocalization in a Two-State DNA-Templated Dye Aggregate System

J Phys Chem A. 2017 Sep 21;121(37):6905-6916. doi: 10.1021/acs.jpca.7b04344. Epub 2017 Sep 6.

Abstract

Coherent exciton delocalization in dye aggregate systems gives rise to a variety of intriguing optical phenomena, including J- and H-aggregate behavior and Davydov splitting. Systems that exhibit coherent exciton delocalization at room temperature are of interest for the development of artificial light-harvesting devices, colorimetric detection schemes, and quantum computers. Here, we report on a simple dye system templated by DNA that exhibits tunable optical properties. At low salt and DNA concentrations, a DNA duplex with two internally functionalized Cy5 dyes (i.e., dimer) persists and displays predominantly J-aggregate behavior. Increasing the salt and/or DNA concentrations was found to promote coupling between two of the DNA duplexes via branch migration, thus forming a four-armed junction (i.e., tetramer) with H-aggregate behavior. This H-tetramer aggregate exhibits a surprisingly large Davydov splitting in its absorbance spectrum that produces a visible color change of the solution from cyan to violet and gives clear evidence of coherent exciton delocalization.

MeSH terms

  • Biomimetic Materials / chemistry
  • Biomimetic Materials / radiation effects
  • Carbocyanines / chemistry*
  • Carbocyanines / radiation effects
  • DNA / chemistry*
  • DNA / radiation effects
  • Energy Transfer
  • Fluorescent Dyes / chemistry*
  • Fluorescent Dyes / radiation effects
  • Kinetics
  • Light
  • Magnesium Chloride / chemistry
  • Models, Chemical
  • Temperature
  • Thermodynamics

Substances

  • Carbocyanines
  • Fluorescent Dyes
  • cyanine dye 5
  • Magnesium Chloride
  • DNA