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Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands

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Abstract

A simple binary synthetic approach with variable [HCOOH]/[Th(IV)] ratios and the addition of water resulted in the self-assembly of six novel thorium formate complexes with well-controlled structures ranging from 0D clusters and 2D layered networks to 3D frameworks. Specifically, small [HCOOH]/[Th(IV)] promoted the formation of the hexanuclear Th6O4(OH)4(HCOO)12 core, a secondary building unit for the construction of 3D [Th6Na(μ3-O)43-OH)4(HCOO)14]·[NH2(CH3)2]·(DMF)3(H2O)5 (Th-SINAP-1), 2D [Th63-O)43-OH)4(HCOO)12(DMF)2]·(H2O)10 (Th-SINAP-2), and 0D [Th63-O)43-OH)4(HCOO)12(H2O)6]·G (Th-SINAP-3). The large [HCOOH]/[Th(IV)] inhibited the olation/oxolation reaction, affording 3D frameworks of [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)2 (Th-SINAP-4), [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)4 (Th-SINAP-5), and [Th2(HCOO)8(H2O)(DMF)]·(H2O)3 (Th-SINAP-6) with monomeric Th(IV) cations as the metal nodes. The addition of water not only affected the hydrolysis of Th(IV) to form nucleophilic hydroxo/oxo-aquo Th species, but also influenced the overall solid-state packing via the competition between H2O, HCOO, OH/O2−, and DMF for coordination with Th4+ cations. This unexpected structural complexity of thorium formates opens a new avenue for the targeted design and synthesis of atypical coordination polymers, e.g. open-framework materials of actinides, for applications in diverse fields such as radionuclide adsorption.

Graphical abstract: Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands

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Publication details

The article was received on 30 Sep 2019, accepted on 30 Oct 2019 and first published on 30 Oct 2019


Article type: Research Article
DOI: 10.1039/C9QI01263J
Inorg. Chem. Front., 2019, Advance Article

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    Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands

    Z. Li, S. Guo, H. Lu, Y. Xu, Z. Yue, L. Weng, X. Guo, J. Lin and J. Wang, Inorg. Chem. Front., 2019, Advance Article , DOI: 10.1039/C9QI01263J

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