2,5-Thiophenedicarboxylate: An interpenetration-inducing ligand in uranyl chemistry

Pierre Thuéry (1) , Jack Harrowfield (2)

1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
2 ISIS - Institut de Science et d'ingénierie supramoléculaires

Seven uranyl ion complexes have been crystallized under solvo-hydrothermal conditions from 2,5thiophenedicarboxylic acid (tdcH2) and diverse additional, structure-directing species. [UO$_2$(tdc)(DMF)]) is a 2-stranded monoperiodic coordination polymer, while [PPh$_3$Me][UO$_2$(tdc)(HCOO)] is a simple chain with terminal formate coligands. Although it is also monoperiodic, [C(NH$_2$)$_3$][H$_2$NMe$_2$]$_2$[(UO$_2$)$_3$(tdc)$_4$(HCOO)] displays an alternation of tetra-and hexanuclear rings. 2-Stranded subunits are bridged by oxo-coordinated Ni$^{II}$ cations to form a diperiodic network in [UO$_2$(tdc)$_2$Ni(cyclam)], but a homometallic sql diperiodic assembly is built in [Cu(R,S-Me$_6$cyclam)(H$_2$O)][UO$_2$(tdc)$_2$]$\cdot$H$_2$O, to which the counterion is hydrogen bonded only. Diperiodic networks with the hcb topology are formed in both [Zn(phen)$_3$][(UO$_2$)$_2$(tdc)$_3$]$\cdot$2H$_2$O$\cdot$3CH$_3$CN and [PPh$_4$]$_2$[(UO$_2$)$_2$(tdc)$_3$]$\cdot$2H$_2$O. The slightly undulating layers in 6 are crossed by oblique columns of weakly interacting counterions in polythreading-like fashion. In contrast, the larger curvature in 7 allows for 3-fold, parallel 2D interpenetration to occur. These results are compared with previously reported cases of interpenetration and polycatenation in the uranyl-tdc$^{2-}$system.

Domains: Cristallography; Coordination chemistry

Pierre Thuéry, Jack Harrowfield. 2,5-Thiophenedicarboxylate: An interpenetration-inducing ligand in uranyl chemistry. Inorganic Chemistry, In press, 60 (12), pp.9074-9083. ⟨10.1021/acs.inorgchem.1c01069⟩. ⟨cea-03258420⟩