Probing the chiroptical response of a single molecule

Chirally sensitive measurement techniques have generally been restricted to bulk samples. Here, we report the observation of fluorescence-detected circular dichroism (FDCD) from single (bridged-triarylamine) helicene molecules by using an excitation wavelength ( 457 nanometers) in the vicinity of an electronic transition that shows circular dichroism in bulk samples. The distributions of dissymmetry ( g) parameters by analysis of signals from pure M- and P-type diastereomers are almost perfect mirror images of one another, each spanning a range of both positive and negative values. In addition, we observe a well-defined structure in the histogram of dissymmetry parameters suggestive of specific molecular orientations at the polymer interface. These single-molecule results highlight strong intrinsic circular dichroism responses that can be obscured by cancellation effects in ensemble measurements of a randomly oriented bulk sample.