A1 Journal article (refereed)
Unsymmetric Chiral Ligands for Large Metallo‐Macrocycles : Selectivity of Orientational Self‐Sorting (2024)

Jurček, O., Chattopadhyay, S., Kalenius, E., Linnanto, J. M., Kiesilä, A., Jurček, P., Radiměřský, P., & Marek, R. (2024). Unsymmetric Chiral Ligands for Large Metallo‐Macrocycles : Selectivity of Orientational Self‐Sorting. Angewandte Chemie, Early online. https://doi.org/10.1002/anie.202409134

JYU authors or editors

Publication details

All authors or editors: Jurček, Ondřej; Chattopadhyay, Subhasis; Kalenius, Elina; Linnanto, Juha M.; Kiesilä, Anniina; Jurček, Pia; Radiměřský, Petr; Marek, Radek

Journal or series: Angewandte Chemie

ISSN: 1433-7851

eISSN: 1521-3773

Publication year: 2024

Publication date: 06/06/2024

Volume: Early online

Publisher: Wiley-VCH Verlag

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/anie.202409134

Publication open access: Openly available

Publication channel open access: Partially open access channel

Abstract

Nature uses various chiral and unsymmetric building blocks to form substantial and complex supramolecular assemblies. In contrary, majority of organic ligands used in metallosupramolecular chemistry are symmetric and achiral. Here we extend on the group of unsymmetric chiral bile acids used as a scaffold for organic bispyridyl ligands employing the chenodeoxycholic acid (CDCA), epimer of previously used ursodeoxycholic acid (UDCA). Ligands’ epimerism, flexibility, and bulkiness leads to large structural differences of coordination products upon reaction with Pd(NO3)2. The UDCA-bispyridyl ligand self-assembles quantitatively into a single crown-like Pd3L6 complex, whereas the CDCA-ligand provides a mixture of coordination complexes of general formula PdnL2n, i.e., Pd2L4, Pd3L6, Pd4L8, Pd5L10, and even Pd6L12 containing impressive 120 chiral centers. The coordination products were studied by a combination of analytical methods, where the ion mobility-mass spectrometry (IM-MS) provided valuable details on their structure and allowed an effective separation of m/z 1461 to individual signals according to arrival time distribution, revealing four different ions of [Pd3L6(NO3)3]3+, [Pd4L8(NO3)4]4+, [Pd5L10(NO3)5]5+, and [Pd6L12(NO3)6]6+. The structures of all complexes were modelled using DFT calculations. Finally, challenges and conclusions in determination of specific structural identity of these unsymmetric species are discussed.

Keywords: coordination complexes; self-assembly (chemistry); asymmetry; supramolecular chemistry

Free keywords: self-assembly; epimerism; chirality; cage compound; supramolecular chemistry

Contributing organizations

Ministry reporting: Yes

Preliminary JUFO rating: 3