Thorium(IV) and Uranium(IV) Complexes with Cucurbit[5]uril

Yingjie Zhang; Mohan Bhadbhade; Maxim Avdeev; Jason R Price; Inna Karatchevtseva; Qing Li; Zhu Tao; Gang Wei

doi:10.1021/acs.inorgchem.8b01347

Thorium(IV) and Uranium(IV) Complexes with Cucurbit[5]uril

Inorg Chem. 2018 Jul 16;57(14):8588-8598. doi: 10.1021/acs.inorgchem.8b01347. Epub 2018 Jun 27.

Authors

Yingjie Zhang¹, Mohan Bhadbhade², Maxim Avdeev¹, Jason R Price³, Inna Karatchevtseva¹, Qing Li⁴, Zhu Tao⁴, Gang Wei⁵

Affiliations

¹ Australian Nuclear Science and Technology Organization , Locked Bag 2001 , Kirrawee DC , NSW 2232 , Australia.
² Mark Wainwright Analytical Centre , University of New South Wales , Kensington , NSW 2052 , Australia.
³ Australian Synchrotron , 800 Blackburn Road , Clayton , VIC 3168 , Australia.
⁴ Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province , Guizhou University , Guiyang , Guizhou 550025 , P. R. China.
⁵ CSIRO Manufacturing , PO Box 218, Lindfield , NSW 2070 , Australia.

PMID: 29949372
DOI: 10.1021/acs.inorgchem.8b01347

Abstract

Tetravalent thorium and uranium complexes with cucurbit[5]uril (Q[5]) were investigated with eight new complexes being synthesized and structurally characterized. [Th(Q[5])(OH)(H₂O)₂]₆·18NO₃· nH₂O (1) has a hexagonal nanowheel structure with each of the six Th⁴⁺ ions being cap-coordinated by a Q[5] and monodentate-coordinated to the nearby Q[5]. [Th(Q[5])(HCOO)(H₂O)₄][Th(NO₃)₅(H₂O)₂]₂[Th(NO₃)₃(HCOO)(H₂O)₂]_0.5·NO₃· nH₂O (2) has a heteroleptic mononuclear structure with a Th⁴⁺ ion cap-coordinated on one side of the Q[5] portal and monodentate-coordinated to a formate anion inside the Q[5] cavity. [KTh_1.5(Q[5])Cl(NO₃)₃][Th(NO₃)₅(H₂O)₂]·2NO₃·2.5H₂O (3) has a heterometallic structure with both Th⁴⁺ and K⁺ ions each occupying one side of the two Q[5] portals forming a capsule. [CsTh(Q[5])Cl(NO₃)₂(H₂O)₃]·2NO₃· nH₂O (4) has a heterometallic 1D polymeric structure with both Th⁴⁺ and Cs⁺ ions each occupying one side of the two Q[5] portals, forming monomers which are linked together by sharing two water molecules and one carbonyl oxygen atom between Th⁴⁺ and Cs⁺ ions. [Th(Q[5])Cl(H₂O)][CdCl₃][CdCl₄]·0.5HCl·4H₂O (5), [Th(Q[5])Cl(H₂O)][Ru₂OCl₉(H₂O)]·0.5HCl·9.5H₂O (6), [Th(Q[5])Cl(H₂O)][IrCl₆]_1.5·3H₂O (7), and [U(Q[5])Cl(H₂O)][ZnCl₃(H₂O)][(ZnCl₄)]·8H₂O (8) have similar 1D polymeric structures with Th⁴⁺/U⁴⁺ ions cap-coordinated on one side of a Q[5] and bidentate coordinated to the nearby Q[5]. The transition metal chlorides act as anions for charge compensation as well as structure inducers via cation-anion interactions forming various anion patterns around the 1D polymers. Actinide contraction has been observed in the early actinide series.