Abstract
One of the striking characteristics of the tris(alkoxo)-ligated Lindqvist-type polyoxovanadates [VV6O13{(OCH2)3CR}2]2- in highest oxidation state in solution is the ease of their chemical post-functionalization via the R group. On surfaces it is their conductivity as a function of individual V(3d) redox states. In both cases, the structural stability of the fully-oxidized dianion is enabled by charge-balancing counterions. In this Article, we explore the charge stability and the charge distibution across the molecular Lindqvist-type hexavanadate structure regarding the R functionality (R = OC2H4N3, CH2N3, and O3C29H36N5) and the different type of countercations (Cat = K+, Li+, NH4+, H+, or Mg2+). We show that the hexavanadate core can accept in its vacant V(3d) orbitals at least four and, in some cases, up to nine additional electrons if the negative charge is offset by the corresponding cation(s), without electron leakage to the covalently attached R groups. Remarkably, the maximum number of accepted electrons strongly depends on the type of cation(s) and is independent on the type of the remote R group exploited herein. The (Cat)n[VV6O13{(OCH2)3CR}2] complexes exibit the structural integrity in all studied charged states. Our study demonstrates the importance of the countercations of multistate polyoxovanadate nanoswitches for the development of multi-charge based molecular memories and/or batteries.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.