Expanding the crystal chemistry of uranyl peroxides: Four hybrid uranyl-peroxide structures containing EDTA

Jie Qiu; Jie Ling; Claire Sieradzki; Kevin Nguyen; Ernest M. Wylie; Jennifer E.S. Szymanowski; Peter C. Burns

doi:10.1021/ic5018906

Expanding the crystal chemistry of uranyl peroxides: Four hybrid uranyl-peroxide structures containing EDTA

Jie Qiu
, Jie Ling
, Claire Sieradzki
, Kevin Nguyen
, Ernest M. Wylie
, Jennifer E.S. Szymanowski
, Peter C. Burns

Research output: Contribution to journal › Article › peer-review

26 Scopus citations

Abstract

The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5-7. Raman spectra demonstrated that reaction solutions that crystallized [NaK₁₅[(UO₂)₈(O₂)₈(C₁₀H₁₂O₁₀N₂)₂(C₂O₄)₄]·(H₂O)₁₄] (1) and [Li₄K₆[(UO₂)₈(O₂)₆(C₁₀H₁₂O₁₀N₂)₂(NO₃)₆]·(H₂O)₂₆] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO₂^4-. The solutions from which [K₄[(UO₂)₄(O₂)₂(C₁₀H₁₃O₈N₂)₂(IO₃)₂]·(H₂O)₁₆] (3) and LiK₃[(UO₂)₄(O₂)₂(C₁₀H₁₂O₈N₂)₂(H₂O)₂]·(H₂O)₁₈ (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA^4-. In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1-4 by EDTA^4- or EDTAO₂^4- results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO₂^4- to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA^4- in 4, forming chains in both cases. In each structure the U-O₂-U dihedral angle is strongly bent, at ∼140°, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides.

Original language	English
Pages (from-to)	12084-12091
Number of pages	8
Journal	Inorganic Chemistry
Volume	53
Issue number	22
DOIs	https://doi.org/10.1021/ic5018906
State	Published - Nov 17 2014
Externally published	Yes

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10.1021/ic5018906

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@article{7877b1cc9320452aa7291da5455e9f54,

title = "Expanding the crystal chemistry of uranyl peroxides: Four hybrid uranyl-peroxide structures containing EDTA",

abstract = "The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5-7. Raman spectra demonstrated that reaction solutions that crystallized [NaK15[(UO2)8(O2)8(C10H12O10N2)2(C2O4)4]·(H2O)14] (1) and [Li4K6[(UO2)8(O2)6(C10H12O10N2)2(NO3)6]·(H2O)26] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO24-. The solutions from which [K4[(UO2)4(O2)2(C10H13O8N2)2(IO3)2]·(H2O)16] (3) and LiK3[(UO2)4(O2)2(C10H12O8N2)2(H2O)2]·(H2O)18 (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA4-. In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1-4 by EDTA4- or EDTAO24- results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO24- to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA4- in 4, forming chains in both cases. In each structure the U-O2-U dihedral angle is strongly bent, at ∼140°, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides.",

author = "Jie Qiu and Jie Ling and Claire Sieradzki and Kevin Nguyen and Wylie, \{Ernest M.\} and Szymanowski, \{Jennifer E.S.\} and Burns, \{Peter C.\}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2014",

month = nov,

day = "17",

doi = "10.1021/ic5018906",

language = "English",

volume = "53",

pages = "12084--12091",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "22",

}

TY - JOUR

T1 - Expanding the crystal chemistry of uranyl peroxides

T2 - Four hybrid uranyl-peroxide structures containing EDTA

AU - Qiu, Jie

AU - Ling, Jie

AU - Sieradzki, Claire

AU - Nguyen, Kevin

AU - Wylie, Ernest M.

AU - Szymanowski, Jennifer E.S.

AU - Burns, Peter C.

PY - 2014/11/17

Y1 - 2014/11/17

N2 - The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5-7. Raman spectra demonstrated that reaction solutions that crystallized [NaK15[(UO2)8(O2)8(C10H12O10N2)2(C2O4)4]·(H2O)14] (1) and [Li4K6[(UO2)8(O2)6(C10H12O10N2)2(NO3)6]·(H2O)26] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO24-. The solutions from which [K4[(UO2)4(O2)2(C10H13O8N2)2(IO3)2]·(H2O)16] (3) and LiK3[(UO2)4(O2)2(C10H12O8N2)2(H2O)2]·(H2O)18 (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA4-. In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1-4 by EDTA4- or EDTAO24- results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO24- to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA4- in 4, forming chains in both cases. In each structure the U-O2-U dihedral angle is strongly bent, at ∼140°, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides.

AB - The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5-7. Raman spectra demonstrated that reaction solutions that crystallized [NaK15[(UO2)8(O2)8(C10H12O10N2)2(C2O4)4]·(H2O)14] (1) and [Li4K6[(UO2)8(O2)6(C10H12O10N2)2(NO3)6]·(H2O)26] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO24-. The solutions from which [K4[(UO2)4(O2)2(C10H13O8N2)2(IO3)2]·(H2O)16] (3) and LiK3[(UO2)4(O2)2(C10H12O8N2)2(H2O)2]·(H2O)18 (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA4-. In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1-4 by EDTA4- or EDTAO24- results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO24- to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA4- in 4, forming chains in both cases. In each structure the U-O2-U dihedral angle is strongly bent, at ∼140°, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides.

UR - https://www.scopus.com/pages/publications/84911091463

U2 - 10.1021/ic5018906

DO - 10.1021/ic5018906

M3 - Article

AN - SCOPUS:84911091463

SN - 0020-1669

VL - 53

SP - 12084

EP - 12091

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

Expanding the crystal chemistry of uranyl peroxides: Four hybrid uranyl-peroxide structures containing EDTA

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