Issue 41, 2019

Dinuclear helicate and tetranuclear cage assembly using appropriately designed ditopic triazole-azine ligands

Abstract

Four new, symmetrical, bis-bidentate ditopic Rdpt-type, Rat (R azine-triazole), ligands have been prepared, Lnpym-meta/para (n = 2 or 4), which contain bidentate n-pyrimidine/triazole binding pockets connected through an appropriate aromatic spacer, meta/para-phenyl, to enable assembly into dinuclear helicates or tetranuclear tetrahedral cages, respectively. The 3 : 2 self assembly reactions of each Lnpym-meta/para ligand with iron(II) tetrafluoroborate gave the desired complexes, as shown by X-ray crystal structure determinations of the pair of helicates [FeII2(Lnpym-meta)3(BF4)4]·6CH3CN, with n = 2 (1·6CH3CN) or 4 (2·6CH3CN), and the pair of Td cages [FeII4(Lnpym-para)6(BF4)8xsolvent, with n = 2 (3·xsolvent) or 4 (4·xsolvent). Reversible FeII/III processes at Em = 0.95 ± 0.05 V vs. 0.01 M AgNO3/Ag in MeCN are a feature of 1–4, with little variation in the redox potential as a function of nuclearity, architecture or choice of n-pyrimidine isomer. In all four complexes the iron(II) centres are low spin, despite having employed the weakest field diazines, the 2- and 4-pyrimidines, in these ditopic Rat ligands. Nevertheless this is an exciting proof of principle that Rdpt-type ligands (previously used to generate about 50 spin crossover-active complexes) can be extended into ditopic forms that are suitable for supramolecular assembly of helicates and cages.

Graphical abstract: Dinuclear helicate and tetranuclear cage assembly using appropriately designed ditopic triazole-azine ligands

Supplementary files

Article information

Article type
Paper
Submitted
06 Тра 2019
Accepted
17 Тра 2019
First published
20 Тра 2019

Dalton Trans., 2019,48, 15435-15444

Dinuclear helicate and tetranuclear cage assembly using appropriately designed ditopic triazole-azine ligands

S. Singh, R. W. Hogue, H. L. C. Feltham and S. Brooker, Dalton Trans., 2019, 48, 15435 DOI: 10.1039/C9DT01890E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements