Cu9O2(VO4)4Cl2, the First Copper Oxychloride Vanadate: Mineralogically Inspired Synthesis and Magnetic Behavior

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Cu9O2(VO4)4Cl2, the First Copper Oxychloride Vanadate: Mineralogically Inspired Synthesis and Magnetic Behavior. / Siidra, Oleg I. ; Vladimirova, Victoria A.; Tsirlin, Alexander A.; Chukanov, Nikita V.; Ugolkov, Valery L.

In: Inorganic Chemistry, Vol. 59, No. 4, 30.01.2020, p. 2136-2143.

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

BibTeX

@article{4e814a92398d4e5c8a6b7a53f0977633,

title = "Cu9O2(VO4)4Cl2, the First Copper Oxychloride Vanadate: Mineralogically Inspired Synthesis and Magnetic Behavior",

abstract = "A new spin-1/2 frustrated antiferromagnet, Cu9O2(VO4)4Cl2, was synthesized via chemical vapor transport method that emulates mineral formation in volcanic fumaroles. Cu9O2(VO4)4Cl2 is the first copper oxychloride vanadate obtained in the ternary CuO–V2O5–CuCl2 anhydrous system. Copper ions constitute a three-dimensional complex framework with a topological structure novel for synthetic compounds but similar to that in the fumarolic mineral yaroshevskite. All of the oxygen atoms except for the O7 site are strongly bonded in the VO4 tetrahedra. The O7 site belongs to an additional oxygen atom (Oa) being tetrahedrally coordinated by four Cu atoms, thus forming the OCu4 tetrahedra. The structural formula can be represented as Cu3[Cu6O2](VO4)4Cl2 highlighting oxocentered units in the structure. IR spectra reveal several absorption bands at 526, 578, and 601 cm–1 interpreted as a characteristic feature of the OCu4 tetrahedra. Cu9O2(VO4)4Cl2 reveals ferrimagnetic behavior with the Curie temperature TC = 24 K and the uncompensated moment of Mr ∼ 1.9 μB/f.u.",

author = "Siidra, {Oleg I.} and Vladimirova, {Victoria A.} and Tsirlin, {Alexander A.} and Chukanov, {Nikita V.} and Ugolkov, {Valery L.}",

note = "Funding Information: This work was financially supported by the Russian Foundation for Basic Research, Grant No. 19-05-00413. Technical support by the SPbSU Resource Centres is gratefully acknowledged. A.A.T. was supported by the Federal Ministry for Education and Research through the Sofja Kovalevskaya Award of the Alexander von Humboldt Foundation. IR spectroscopy studies (N.V.C.) were performed as a part of State Task No. 0089-2019-0013.",

year = "2020",

month = jan,

day = "30",

doi = "10.1021/acs.inorgchem.9b02565",

language = "English",

volume = "59",

pages = "2136--2143",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

RIS

TY - JOUR

T1 - Cu9O2(VO4)4Cl2, the First Copper Oxychloride Vanadate: Mineralogically Inspired Synthesis and Magnetic Behavior

AU - Siidra, Oleg I.

AU - Vladimirova, Victoria A.

AU - Tsirlin, Alexander A.

AU - Chukanov, Nikita V.

AU - Ugolkov, Valery L.

N1 - Funding Information: This work was financially supported by the Russian Foundation for Basic Research, Grant No. 19-05-00413. Technical support by the SPbSU Resource Centres is gratefully acknowledged. A.A.T. was supported by the Federal Ministry for Education and Research through the Sofja Kovalevskaya Award of the Alexander von Humboldt Foundation. IR spectroscopy studies (N.V.C.) were performed as a part of State Task No. 0089-2019-0013.

PY - 2020/1/30

Y1 - 2020/1/30

N2 - A new spin-1/2 frustrated antiferromagnet, Cu9O2(VO4)4Cl2, was synthesized via chemical vapor transport method that emulates mineral formation in volcanic fumaroles. Cu9O2(VO4)4Cl2 is the first copper oxychloride vanadate obtained in the ternary CuO–V2O5–CuCl2 anhydrous system. Copper ions constitute a three-dimensional complex framework with a topological structure novel for synthetic compounds but similar to that in the fumarolic mineral yaroshevskite. All of the oxygen atoms except for the O7 site are strongly bonded in the VO4 tetrahedra. The O7 site belongs to an additional oxygen atom (Oa) being tetrahedrally coordinated by four Cu atoms, thus forming the OCu4 tetrahedra. The structural formula can be represented as Cu3[Cu6O2](VO4)4Cl2 highlighting oxocentered units in the structure. IR spectra reveal several absorption bands at 526, 578, and 601 cm–1 interpreted as a characteristic feature of the OCu4 tetrahedra. Cu9O2(VO4)4Cl2 reveals ferrimagnetic behavior with the Curie temperature TC = 24 K and the uncompensated moment of Mr ∼ 1.9 μB/f.u.

AB - A new spin-1/2 frustrated antiferromagnet, Cu9O2(VO4)4Cl2, was synthesized via chemical vapor transport method that emulates mineral formation in volcanic fumaroles. Cu9O2(VO4)4Cl2 is the first copper oxychloride vanadate obtained in the ternary CuO–V2O5–CuCl2 anhydrous system. Copper ions constitute a three-dimensional complex framework with a topological structure novel for synthetic compounds but similar to that in the fumarolic mineral yaroshevskite. All of the oxygen atoms except for the O7 site are strongly bonded in the VO4 tetrahedra. The O7 site belongs to an additional oxygen atom (Oa) being tetrahedrally coordinated by four Cu atoms, thus forming the OCu4 tetrahedra. The structural formula can be represented as Cu3[Cu6O2](VO4)4Cl2 highlighting oxocentered units in the structure. IR spectra reveal several absorption bands at 526, 578, and 601 cm–1 interpreted as a characteristic feature of the OCu4 tetrahedra. Cu9O2(VO4)4Cl2 reveals ferrimagnetic behavior with the Curie temperature TC = 24 K and the uncompensated moment of Mr ∼ 1.9 μB/f.u.

UR - http://www.scopus.com/inward/record.url?scp=85079201094&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.9b02565

DO - 10.1021/acs.inorgchem.9b02565

M3 - Article

VL - 59

SP - 2136

EP - 2143

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 4

ER -

ID: 52290016