Enantioenriched Ruthenium-Tris-Bipyridine Complexes Bearing One Helical Bipyridine Ligand: Access to Fused Multihelicenic Systems and Chiroptical Redox Switches

Kos, Martin; Rodríguez, Rafael; Storch, Jan; Sýkora, Jan; Caytan, Elsa; Cordier, Marie; Císařová, Ivana; Vanthuyne, Nicolas; Williams, J.A. Gareth; Žádný, Jaroslav; Církva, Vladimír; Crassous, Jeanne

doi:10.1021/acs.inorgchem.1c01379

Enantioenriched Ruthenium-Tris-Bipyridine Complexes Bearing One Helical Bipyridine Ligand: Access to Fused Multihelicenic Systems and Chiroptical Redox Switches

Kos, Martin; Rodríguez, Rafael; Storch, Jan; Sýkora, Jan; Caytan, Elsa; Cordier, Marie; Císařová, Ivana; Vanthuyne, Nicolas; Williams, J.A. Gareth; Žádný, Jaroslav; Církva, Vladimír; Crassous, Jeanne

Authors

Martin Kos

Rafael Rodríguez

Jan Storch

Jan Sýkora

Elsa Caytan

Marie Cordier

Ivana Císařová

Nicolas Vanthuyne

Professor Gareth Williams j.a.g.williams@durham.ac.uk
Professor

Jaroslav Žádný

Vladimír Církva

Jeanne Crassous

Abstract

The synthesis and photophysical and chiroptical properties of novel aza[n]helicenes (6a–d, 10a,b, n = 4–7) substituted with one or two 2-pyridyl groups are described. The preparation was performed via an adapted Mallory reaction using aromatic imines as precursors. The obtained novel class of helical 2,2′-bipyridine ligands was then coordinated to Ru(bipy)22+ units, thus affording the first diastereomerically and enantiomerically pure [RuL(bipy)2]2+ (11a,c, L = 6a,c) or [Ru2L′(bipy)4]4+ (12, L′ = 10b) complexes. The topology and stereochemistry of these novel metal-based helical architectures were studied in detail, notably using X-ray crystallography. Interestingly, the coordination to ruthenium(II) enabled the preparation of fused multihelical systems incorporating aza- and ruthena-helicenes within the same scaffold. The photophysical, chiroptical, and redox properties of these complexes were examined in detail, and efficient redox-triggered chiroptical switching activity was evidenced.

Citation

Kos, M., Rodríguez, R., Storch, J., Sýkora, J., Caytan, E., Cordier, M., …Crassous, J. (2021). Enantioenriched Ruthenium-Tris-Bipyridine Complexes Bearing One Helical Bipyridine Ligand: Access to Fused Multihelicenic Systems and Chiroptical Redox Switches. Inorganic Chemistry, https://doi.org/10.1021/acs.inorgchem.1c01379

Journal Article Type	Article
Acceptance Date	Jun 29, 2021
Online Publication Date	Jul 23, 2021
Publication Date	2021
Deposit Date	Jul 26, 2021
Publicly Available Date	Jul 23, 2022
Journal	Inorganic Chemistry
Print ISSN	0020-1669
Electronic ISSN	1520-510X
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
DOI	https://doi.org/10.1021/acs.inorgchem.1c01379

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.1c01379