UV-vis and ECD spectroelectrochemistry of atropisomeric naphthalenediimide derivative

Krzysztof Karoń; Joanna E Rode; Dorota Kaczorek; Robert Kawęcki; Sandra Pluczyk-Małek; Mieczysław Łapkowski; Sławomir Ostrowski; Krzysztof Lyczko; Jan Cz Dobrowolski

doi:10.1016/j.saa.2022.122089

UV-vis and ECD spectroelectrochemistry of atropisomeric naphthalenediimide derivative

Spectrochim Acta A Mol Biomol Spectrosc. 2023 Mar 5:288:122089. doi: 10.1016/j.saa.2022.122089. Epub 2022 Nov 10.

Authors

Krzysztof Karoń¹, Joanna E Rode², Dorota Kaczorek³, Robert Kawęcki³, Sandra Pluczyk-Małek⁴, Mieczysław Łapkowski⁵, Sławomir Ostrowski⁶, Krzysztof Lyczko⁶, Jan Cz Dobrowolski⁷

Affiliations

¹ Faculty of Chemistry, Silesian University of Technology, 9 Strzody Street, 44-100 Gliwice, Poland; Centre for Organic and Nanohybrid Electronics, Silesian University of Technology, 22b Konarskiego Street, 44-100 Gliwice, Poland. Electronic address: krzysztof.karon@polsl.pl.
² Laboratory for Spectroscopy, Molecular Modeling and Structure Determination, Institute of Nuclear Chemistry and Technology, 16 Dorodna Street, 03-195 Warsaw, Poland. Electronic address: j.rode@ichtj.waw.pl.
³ Faculty of Science, Siedlce University, 3 Maja Street No 54, 08-110 Siedlce, Poland.
⁴ Faculty of Chemistry, Silesian University of Technology, 9 Strzody Street, 44-100 Gliwice, Poland; Centre for Organic and Nanohybrid Electronics, Silesian University of Technology, 22b Konarskiego Street, 44-100 Gliwice, Poland.
⁵ Faculty of Chemistry, Silesian University of Technology, 9 Strzody Street, 44-100 Gliwice, Poland; Centre for Organic and Nanohybrid Electronics, Silesian University of Technology, 22b Konarskiego Street, 44-100 Gliwice, Poland; Centre of Polymer and Carbon Materials, Polish Academy of Science, 34 Curie Sklodowska Street, 41-800 Zabrze, Poland.
⁶ Laboratory for Spectroscopy, Molecular Modeling and Structure Determination, Institute of Nuclear Chemistry and Technology, 16 Dorodna Street, 03-195 Warsaw, Poland.
⁷ Laboratory for Spectroscopy, Molecular Modeling and Structure Determination, Institute of Nuclear Chemistry and Technology, 16 Dorodna Street, 03-195 Warsaw, Poland. Electronic address: j.dobrowolski@nil.gov.pl.

PMID: 36436264
DOI: 10.1016/j.saa.2022.122089

Abstract

The UV-vis and ECD spectroelectrochemistry (SEC) of a chiral binaphthalenylamine derivative of the N-butyl naphthalenediimide (NDIB-NH₂) enantiomers were applied to measure UV-vis and ECD spectra of NDIB-NH₂ radicals and dianion formed in the reduction and oxidation processes observed in cyclic voltammetry (CV). The CV curves and EPR spectroelectrochemistry enabled us to establish conditions at which a radical-anion [NDIB-NH₂]̇^.-, a dianion [NDIB-NH₂]^2-, and a radical-cation [NDIB-NH₂]̇^.+ are formed. The DFT restricted open-shell CAM-B3LYP-D3/def2TZVP/PCM calculations demonstrated that in the radical-anion [NDIB-NH₂]̇^.^-, spin is spread over the NDI system while in the radical-cation [NDIB-NH₂]̇⁺ it is spread over the aminonaphthalene moiety. The UV-vis spectra of radical-anion and dianion show the most significant changes in the 400-800 nm range. In that range, the ECD spectra varied with the change of electrode potential more than the UV-vis did and enabled the identification of a new ECD band of [NDIB-NH₂]̇^.^- at ca. 400 nm hidden in the background in the UV spectra at -1000 mV. A broad structured ECD pattern with a maximum at ca. 530 nm was observed for [NDIB-NH₂]̇^.^- (-1000 mV), while a single smooth ECD band of [NDIB-NH₂]^2- was located at 520 nm (-1750 mV). For the first time, an isosbestic point (455 nm) was found in ECD spectroelectrochemical measurements for the radical-cation [NDIB-NH₂]̇^.⁺ in equilibrium with the NDIB-NH₂ neutral form. The TD-DFT CAM-B3LYP-D3/6-31G** calculations combined with the hybrid (explicit combined with implicit) solvation model fairly well reproduced the UV-vis and ECD SEC of neutral and redox forms of NDIB-NH₂ but the ECD spectrum of [NDIB-NH₂]̇^.⁺ above 390 nm.

Keywords: Cyclic voltammetry; ECD SEC; EPR; Hybrid solvation; Isosbestic point; TD-DFT.

MeSH terms

Anions
Cations
Density Functional Theory*
Oxidation-Reduction

Substances

naphthalenediimide
Anions
Cations