Reactivity Studies of a Dipyridine Ethinyl Ligand with Zinc(II)

• Published in: European journal of inorganic chemistry Vol. 2019; no. 48; pp. 5059 - 5065
• Main Authors: Egger, Christiane M., Jakob, Christian H. G., Kaiser, Felix, Rindle, Olivia, Altmann, Philipp J., Reich, Robert M., Kühn, Fritz E.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 31.12.2019; Wiley Subscription Services, Inc
• Subjects: Acetonitrile; Chemistry; Chemistry, Inorganic & Nuclear; Coordination polymers; Functional groups; Inorganic chemistry; Ligand effects; Ligands; N ligands; Physical Sciences; Protecting groups; Sandwich structures; Science & Technology; Zinc; Zinc coordination; Coordination polymers; DESIGN; M2L4 MOLECULAR CAPSULES; COMPLEXES; CRYSTAL-STRUCTURES; LUMINESCENT PROPERTIES; Zinc; HYDROTHERMAL SYNTHESIS; DELIVERY; MACROMOLECULAR THERAPEUTICS; N ligands; METAL-ORGANIC FRAMEWORKS; Protecting groups; Ligand effects
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201900984

Several dipyridine ethinyl ligands bearing a variety of functional groups (OMe, COOH, NH2, NHBoc, NBoc2) were synthesized and reacted with Zn(OTf)2 in CH3CN. Fundamental studies towards the reaction behavior between zinc and these ligands were conducted, showing that ligands with an amine group and its Boc protected derivatives (NBoc2 and NHBoc) lead to isolable defined products. SC‐XRD of the product derived from the amine ligand reveals a polymeric sandwich structure, showing that the NH2 moiety seems to be of vital importance for product formation. Depending on the reaction temperature, two novel coordination polymers are obtained upon reaction of the Boc protected amine ligands with Zn(OTf)2 in acetonitrile. SC‐XRD reveals for the NHBoc ligand an one‐dimensional CP with a layer structure, whereas the NBoc2 moiety possesses a two‐dimensional layer structure, with the NBoc2 moiety acting as a chelator for zinc(II) within the coordination polymer. An overall reactivity study of dipyridine ethinyl ligands with zinc(II) leads to three different novel coordination polymers, depending on the reaction temperature. Showing an unprecedented coordination mode, i.e. a di‐boc group acting as a chelator for zinc(II).