Fluorescence Polarization Measurements to Probe Alignment of a Bithiophene Dye in One-Dimensional Channels of Self-Assembled Phenylethynylene Bis-Urea Macrocycle Crystals

5 years ago

Fluorescence Polarization Measurements to Probe Alignment of a Bithiophene Dye in One-Dimensional Channels of Self-Assembled Phenylethynylene Bis-Urea Macrocycle Crystals

Linda S. Shimizu, Andrew B. Greytak, Frank Würthner, Bozumeh Som, Preecha Kittikhunnatham, Matthias Stolte, Vitaly Rassolov

This paper describes the use of polarized fluorescence microscopy to directly probe guest molecule orientation in bis-urea macrocycle crystals. These macrocycles assemble to afford one-dimensional (1D) microchannels ∼9 Å in diameter that have previously been shown to exhibit normal Fickian diffusion and induce selective reactivity among the confined guest molecules. In the present work, we take advantage of the quasi-1D morphology of fiber-like microcrystals with the extended dimension corresponding to the channel axis to measure excitation and emission polarization values for a bithiophene guest. Guest fluorescence is shown to be polarized along the fiber axis with emission polarization values up to 0.729, indicating a high degree of orientational order within the 1D channels. The observed behavior is consistent with calculated results for the guest orientation and electronic transition dipole moment. The results indicate the value of functional fluorescent probes as a measure of guest confinement in low-dimensional environments.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b07136

DOI: 10.1021/acs.jpcc.7b07136