Issue 40, 2019, Issue in Progress

Time-controlled synthesis of the 3D coordination polymer U(1,2,3-Hbtc)2 followed by the formation of molecular poly-oxo cluster {U14} containing hemimellitate uranium(iv)

Abstract

Two coordination compounds bearing tetravalent uranium were synthesized in the presence of tritopic hemimellitic acid in acetonitrile with a controlled amount of water (H2O/U ≈ 8) and structurally characterized. Compound 1, [U(1,2,3-Hbtc)2]·0.5CH3CN is constructed around an eight-fold coordinated uranium cationic unit [UO8] linked by the poly-carboxylate ligands to form dimeric subunits, which are further connected to form infinite corrugated ribbons and a three-dimensional framework. Compound 2, [U14O8(OH)4Cl8(H2O)16(1,2,3-Hbtc)8(ox)4(ac)4] ({U14}) exhibits an unprecedented polynuclear {U14} poly-oxo uranium cluster surrounded by O-donor and chloride ligands. It is based on a central core of [U6O8] type surrounded by four dinuclear uranium-subunits {U2}. Compound 1 was synthesized by a direct reaction of hemimellitic acid with uranium tetrachloride in acetonitrile (+H2O), while the molecular species ({U14} (2)) crystallized from the supernatant solution after one month. The slow hydrolysis reaction together with the partial decomposition of the starting organic reactants into oxalate and acetate molecules induces the generation of such a large poly-oxo cluster with fourteen uranium centers. Structural comparisons with other closely related uranium-containing clusters, such as the {U12} cluster based on the association of inner core [U6O8] with three dinuclear sub-units {U2}, were performed.

Graphical abstract: Time-controlled synthesis of the 3D coordination polymer U(1,2,3-Hbtc)2 followed by the formation of molecular poly-oxo cluster {U14} containing hemimellitate uranium(iv)

Supplementary files

Article information

Article type
Paper
Submitted
16 May 2019
Accepted
15 Jul 2019
First published
23 Jul 2019
This article is Open Access
Creative Commons BY-NC license

RSC Adv., 2019,9, 22795-22804

Time-controlled synthesis of the 3D coordination polymer U(1,2,3-Hbtc)2 followed by the formation of molecular poly-oxo cluster {U14} containing hemimellitate uranium(IV)

M. Dufaye, N. P. Martin, S. Duval, C. Volkringer, A. Ikeda-Ohno and T. Loiseau, RSC Adv., 2019, 9, 22795 DOI: 10.1039/C9RA03707A

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, 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 commercial 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