Skip to Main content Skip to Navigation
New interface
Journal articles

Plumbing the uncertainties of solvothermal synthesis involving uranyl ion carboxylate complexes.

Jack Harrowfield 1 Youssef Atoini 1 Pierre Thuéry 2 
2 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)
Abstract : Some of the uncertainties inherent to solvo-hydrothermal synthetic methods which often hinder isolation of the desired product are discussed and illustrated by the structural characterisation of four uranyl ion complexes with long-chain saturated or unsaturated aliphatic dicarboxylate ligands, this being placed in the context of previous results. [Zn(phen)$_2$(HCOO)][UO$_2$(muc)(HCOO)] (1), where H$_2$muc is trans,trans-muconic (trans,trans-1,6-hexa-2,4-dienedioic) acid, includes formate anions, generated in situ from N,N-dimethylformamide (DMF) hydrolysis, as chelating ligands on both metal centres, which limits polymer periodicity. [UO$_2$(muc)(NMP)] (2) was obtained in the presence of PPh$_4 ^+$ cations, but coordination of N-methyl-2-pyrrolidone (NMP) results in formation of a neutral monoperiodic polymer instead of an anionic one. Similarly, NMP complexation prevents inclusion of [Co(en)$_3$]$^{3+}$ cations in [UO$_2$(C8)(NMP)] (3), where H$_2$C8 is 1,8-octanedioic acid, another monoperiodic coordination polymer. No solvent is coordinated in [H$_2$NMe$_2$]$_2$[(UO$_2$)2(C13)$_3$] (4), where H$_2$C13 is 1,13-tridecanedioic acid, but the desired [Co(en)$_3$]$^{3+}$ counterions are displaced by H$_2$NMe$_2^{2+}$ cations generated in situ from DMF hydrolysis, giving a diperiodic network with the KIa topological type, isomorphous to that formed from 1,15-pentadecanedioic acid. Complexes 1 and 2 are non-emissive in the solid state, while 4 displays a broad uranyl emission peak with unresolved fine structure.
Document type :
Journal articles
Complete list of metadata

https://hal-cea.archives-ouvertes.fr/cea-03543383
Contributor : Serge Palacin Connect in order to contact the contributor
Submitted on : Wednesday, January 26, 2022 - 7:44:29 AM
Last modification on : Tuesday, September 27, 2022 - 4:27:38 AM
Long-term archiving on: : Wednesday, April 27, 2022 - 6:12:46 PM

File

Thuery_CrystEngComm2022a_V0.pd...
Files produced by the author(s)

Identifiers

Citation

Jack Harrowfield, Youssef Atoini, Pierre Thuéry. Plumbing the uncertainties of solvothermal synthesis involving uranyl ion carboxylate complexes.. CrystEngComm, 2022, 24, pp.1475-1484. ⟨10.1039/D1CE01663F⟩. ⟨cea-03543383⟩

Share

Metrics

Record views

30

Files downloads

50