Thorium(IV) and Uranium(IV) Complexes with Cucurbit[8]Uril: Supramolecular Structures Via Direct Coordination and Second-Shell Interactions

26 Pages Posted: 1 Jun 2020

See all articles by Yingjie Zhang

Yingjie Zhang

Government of the Commonwealth of Australia - Australian Nuclear Science and Technology Organisation

Inna Karatchevtseva

affiliation not provided to SSRN

Ming Liu

Guizhou University

Zhu Tao

affiliation not provided to SSRN

Gang Wei

CSIRO

Abstract

With the increase of portal size and cavity, cucurbit[n]urils {Q[n]s, n = 5-8} tend to have richer host-guest chemistry and less affinity for metal complexation. As such no any tetravalent actinide complex of Q[8] has ever been reported. In this work, we studied thorium(IV) and uranium(IV) complexes of Q[8] in HCl solutions with the addition of various transition metal chlorides as structure inducers. Consequently, three complexes with similar supramolecular structures built up with both direct coordination and second-shell interactions have been synthesized and structurally characterized. In the presence of CdCl2/RuCl3, {[ThCl(H2O)6]2(Q[8])}·(Q[8])·2(CdCl4)·2Cl·6H2O (Q[8]-Th-Cd) or {[Th(H2O)7]2(Q[8])}·(Q[8])·2(RuCl5)2O·3(HCl)·22H2O (Q[8]-Th-Ru) were synthesized while {[U(H2O)7]2(Q[8])}·(Q[8])·5(ZnCl4)·8H2O (Q[8]-U-Zn) was prepared with U(IV) ions generated in situ by direct reduction of uranyl nitrate with zinc metal. All three complexes have Q[8] directly coordinated to Th(IV)/U(IV) ions, one on each side of the two portals in bidentate mode. Subsequent second-shell interactions between (Th2-Q[8])/(U2-Q[8]) complexes and Q[8] molecules form one-dimensional polymers which are further connected through CH···Cl [Cd/Ru/Zn chloride species] interactions forming extended supramolecular networks.

Keywords: thorium, uranium, cucurbit[8]uril, supramolecular, structure, X-ray diffraction

Suggested Citation

Zhang, Yingjie and Karatchevtseva, Inna and Liu, Ming and Tao, Zhu and Wei, Gang, Thorium(IV) and Uranium(IV) Complexes with Cucurbit[8]Uril: Supramolecular Structures Via Direct Coordination and Second-Shell Interactions. Available at SSRN: https://ssrn.com/abstract=3615149

Yingjie Zhang (Contact Author)

Government of the Commonwealth of Australia - Australian Nuclear Science and Technology Organisation ( email )

Locked Bag 2001
Kirrawee DC
Sydney, New South Wales NSW 2232
Australia

Inna Karatchevtseva

affiliation not provided to SSRN

No Address Available

Ming Liu

Guizhou University

Guizhou
China

Zhu Tao

affiliation not provided to SSRN

No Address Available

Gang Wei

CSIRO

Black Mountain
Canberra
Australia

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