Catechol Thioesters: Ligands for Hierarchically Formed Lithium‐Bridged Titanium(IV) Helicates and Helicate‐Based Switches. Issue 17 (5th March 2020)

• Record Type: Journal Article
• Authors: Kwamen, A. Carel N.; de Macedo, Gilles S.; Wiederhold, Constanze; Oppel, Iris M.; Albrecht, Markus
• Is Part Of: Chemistry. Volume 26:Issue 17(2020)
• Page Start: 3829
• Page End: 3833
• Publication Date: 2020-03-05
• Subjects: helicates -- molecular switches -- self-assembly -- thermodynamics -- titanium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201905212
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The thioester moiety is introduced as a lithium binding unit for the hierarchical formation of titanium(IV) catecholate‐based lithium‐bridged helicates. In solution, the coordination compounds show a monomer–dimer equilibrium which —in comparison to the oxo esters— is significantly shifted towards the monomers. In addition, the influence of the thioester side chain on the dimerization behavior is investigated and an expansible/compressible molecular switch is synthesized. In the latter case expansion and compression are performed reversibly in methanol, whereas in DMSO spontaneous expansion occurs. Abstract : Titanium springs : Titanium (IV) triscatechol thioester complexes form in the presence of lithium cations dinuclear helicates, showing a monomer–dimer equilibrium with dimerization tendencies lying between those of the corresponding ketones and oxoesters. Based on this principle, it is possible to obtain a switchable spring‐type helicate which shows some spontaneous expansion in [D6 ]DMSO.