Unsymmetric Chiral Ligands for Large Metallo-Macrocycles: Selectivity of Orientational Self-Sorting.

Autor: Jurček O; Department of Natural Drugs, Faculty of Pharmacy, Masaryk University, Palackého 1946/1, CZ-61200, Brno, Czechia.; Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, CZ-62500, Brno, Czechia.; CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, CZ-62500, Brno, Czechia., Chattopadhyay S; Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, CZ-62500, Brno, Czechia.; CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, CZ-62500, Brno, Czechia., Kalenius E; Department of Chemistry, University of Jyvaskyla P. O. Box 35, FI-40014, Jyväskylä, Finland., Linnanto JM; Institute of Physics, University of Tartu, W. Ostwald Street 1, 50411, Tartu, Estonia., Kiesilä A; Department of Chemistry, University of Jyvaskyla P. O. Box 35, FI-40014, Jyväskylä, Finland., Jurček P; CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, CZ-62500, Brno, Czechia., Radiměřský P; Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, CZ-62500, Brno, Czechia., Marek R; Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, CZ-62500, Brno, Czechia.; CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, CZ-62500, Brno, Czechia.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Sep 02; Vol. 63 (36), pp. e202409134. Date of Electronic Publication: 2024 Aug 01.
DOI: 10.1002/anie.202409134
Abstrakt: Nature uses various chiral and unsymmetric building blocks to form substantial and complex supramolecular assemblies. In contrast, the majority of organic ligands used in metallosupramolecular chemistry are symmetric and achiral. Here we extend the group of unsymmetric chiral bile acids used as a scaffold for organic bispyridyl ligands by employing chenodeoxycholic acid (CDCA), an epimer of the previously used ursodeoxycholic acid (UDCA). The epimerism, flexibility, and bulkiness of the ligands leads to large structural differences in coordination products upon reaction with Pd(NO 3 ) 2 . The UDCA-bispyridyl ligand self-assembles quantitatively into a single crown-like Pd 3 L 6 complex, whereas the CDCA ligand provides a mixture of coordination complexes of general formula Pd n L 2n , i.e., Pd 2 L 4 , Pd 3 L 6 , Pd 4 L 8 , Pd 5 L 10 , and even Pd 6 L 12 containing an impressive 120 chiral centers. The coordination products were studied by a combination of analytical methods, with ion-mobility mass spectrometry (IM-MS) providing valuable details on their structure and allowed an effective separation of m/z 1461 to individual signals according to the arrival time distribution, thereby revealing four different ions of [Pd 3 L 6 (NO 3 ) 3 ] 3+ , [Pd 4 L 8 (NO 3 ) 4 ] 4+ , [Pd 5 L 10 (NO 3 ) 5 ] 5+ , and [Pd 6 L 12 (NO 3 ) 6 ] 6+ . The structures of all the complexes were modelled using DFT calculations. Finally, the challenges and conclusions in determining the specific structural identity of these unsymmetric species are discussed.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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