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Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes.

Published version
Peer-reviewed

Type

Article

Change log

Authors

García-Romero, Álvaro 
Martín-Álvarez, Jose M  ORCID logo  https://orcid.org/0000-0002-6969-0703
Álvarez, Celedonio M  ORCID logo  https://orcid.org/0000-0003-4431-6501

Abstract

The use of antimony and bismuth in supramolecular chemistry has been largely overlooked in comparison to the lighter elements of Group 15, and the coordination chemistry of the tripodal ligands [Sb(3-py)3] and [Bi(3-py)3] (L) containing the heaviest p-block element bridgehead atoms has been unexplored. We show that these ligands form a common hybrid metal-organic framework (MOF) structure with Cu(I) and Ag(I) (M) salts of weakly coordinating anions (PF6-, SbF6-, and OTf-), composed of a cationic substructure of rhombic cage (M)4(L)4 units linked by Sb/Bi-M bonding. The greater Lewis acidity of Bi compared to Sb can, however, allows anion···Bi interactions to overcome Bi-metal bonding in the case of BF4-, leading to collapse of the MOF structure (which is also seen where harder metals like Li+ are employed). This study therefore provides insight into the way in which the electronic effects of the bridgehead atom in these ligand systems can impact their supramolecular chemistry.

Description

Funder: Universidad de Valladolid

Keywords

3402 Inorganic Chemistry, 3403 Macromolecular and Materials Chemistry, 34 Chemical Sciences

Journal Title

Inorg Chem

Conference Name

Journal ISSN

0020-1669
1520-510X

Volume Title

60

Publisher

American Chemical Society (ACS)
Sponsorship
Agencia Estatal de Investigaci??n, Ministerio de Ciencia, Innovaci??n y Universidades (PGC2018-096880-A-I00, PGC2018-099470-B-I00)
Leverhulme Trust (RPG-2017-146)
Ministerio de Econom??a y Competitividad (RYC-201519035)