Chiral Porphyrin Assemblies Investigated by a Modified Reflectance Anisotropy Spectroscopy Spectrometer

Abstract

Reflectance anisotropy spectroscopy (RAS) has been largely used to investigate organic compounds: Langmuir–Blodgett and Langmuir–Schaeffer layers, the organic molecular beam epitaxy growth in situ and in real time, thin and ultrathin organic films exposed to volatiles, in ultra-high vacuum (UHV), in controlled atmosphere and even in liquid. In all these cases, porphyrins and porphyrin-related compounds have often been used, taking advantage of the peculiar characteristics of RAS with respect to other techniques. The technical modification of a RAS spectrometer (CD-RAS: circular dichroism RAS) allows us to investigate the circular dichroism of samples instead of the normally studied linear dichroism: CD-RAS measures (in transmission mode) the anisotropy of the optical properties of a sample under right and left circularly polarized light. Although commercial spectrometers exist to measure the circular dichroism of substances, the “open structure” of this new spectrometer and its higher flexibility in design makes it possible to couple it with UHV systems or other experimental configurations. The importance of chirality in the development of organic materials (from solutions to the solid state, as thin layers deposited—in liquid or in vacuum—on transparent substrates) could open interesting possibilities to a development in the investigation of the chirality of organic and biological layers. In this manuscript, after the detailed explanation of the CD-RAS technique, some calibration tests with chiral porphyrin assemblies in solution or deposited in solid film are reported to demonstrate the quality of the results, comparing curves obtained with CD-RAS and a commercial spectrometer.

Porphyrin-Based Compounds: Synthesis and Application

“…Golleti and co-workers [27] highlighted the importance of chirality in organic materials, using Reflectance Anisotropy Spectroscopy (RAS) to investigate porphyrins and porphyrin-related compounds, in various experimental conditions, including ultra-high vacuum-controlled atmospheres and liquid. The study introduced a technical enhancement to the RAS spectrometer called CD-RAS (circular dichroism RAS), which allows for the measurement of circular dichroism (CD) in samples under right-and left-circularly polarized light in transmission mode, offering flexibility and potential applications in various experimental setups.…”