An optically transparent thin-layer electrochemical cell for the study of vibrational circular dichroism of chiral redox-active molecules

Abstract

An optically transparent thin-layer electrochemical cell for the study of vibrational circular dichroism of chiral redox-active molecules Domingos, S.R.; Luyten, H.; van Anrooij, F.; Sanders, H. J.; Bakker, B.H.; Buma, W.J.; Hartl, F.; Woutersen, S. General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. An optically transparent thin-layer electrochemical (OTTLE) cell with a locally extended optical path has been developed in order to perform vibrational circular dichroism (VCD) spectroscopy on chiral molecules prepared in specific oxidation states by means of electrochemical reduction or oxidation. The new design of the electrochemical cell successfully addresses the technical challenges involved in achieving sufficient infrared absorption. The VCD-OTTLE cell proves to be a valuable tool for the investigation of chiral redox-active molecules.

Elucidating the Structure of Chiral Molecules by using Amplified Vibrational Circular Dichroism: From Theory to Experimental Realization

“…For this purpose, an optically transparent thin‐layer electrochemical cell (OTTLE) was designed and constructed to perform spectroelectrochemical‐VCD measurements using a commercially available VCD spectrometer. The technical details of the experimental setup can be found elsewhere …”

Elucidating the Structure of Chiral Molecules by using Amplified Vibrational Circular Dichroism: From Theory to Experimental Realization

“…[21] For this purpose, an optically transparent thin-layere lectrochemical cell (OTTLE) was designed and constructedt op erform spectroelectrochemical-VCD measurements using ac ommercially availableV CD spectrometer.T he technical details of the experimental setup can be found elsewhere. [22] To investigate the effect of electrochemical reduction on the VCD response,c ompounds (S)-and (R)-methyl 2-(1,3-dioxo-1Hbenzo[de]isoquinolin-2(3H)-yl)propanoate ((S)-1 and (R)-1 respectively,s ee Figure5)w ere investigated in both the neutral and radical anion forms, using UV/Vis, IR and VCD spectroscopy.A se xpected, the UV/Vis absorption spectrum ( Figure 6) of the radical anion shows absorption bands at much longer wavelengths than the corresponding spectrum of the neutral compound. The observed electronic structure wasc onfirmed by time-dependent density-functionaltheory calculations.…”

Switchable Amplification of Vibrational Circular Dichroism as a Probe of Local Chiral Structure

“…For this specific purpose, we chose ferrocene (Fc) as the external VCD amplifier. [33] The relative ease with which this unit can be incorporated at specific locations within a larger molecular system makes it well suited for probing local structure with VCD. In contrast, the one-electron-oxidized ferrocenium cation has an open-shell configuration (Fe 3+ ) with low-lying electronically excited states, which strongly enhance VCD.…”