Perovzalates: a family of perovskite-related oxalates

Rebecca Clulow; Alasdair J. Bradford; Stephen L. Lee; Philip Lightfoot

doi:10.1039/c9dt03149a

Perovzalates: a family of perovskite-related oxalates

Rebecca Clulow, Alasdair J. Bradford, Stephen L. Lee, Philip Lightfoot

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Abstract

A family of hybrid Perovskite-oxalates (“Perovzalates”) of general composition A^ILi₃M^II(C₂O₄)₃ (A = K⁺, Rb⁺, Cs⁺; M = Fe²⁺, Co²⁺, Ni²⁺) are presented. All eight new compounds are isostructural with the previously reported examples NH₄Li₃Fe(C₂O₄)₃ and KLi₃Fe(C₂O₄)₃, crystallising in the rhombohedral space group Rc, with a ∼11.3–11.6 Å, c ∼14.8–15.2 Å. In contrast to other families of “hybrid perovskites” such as the formates, these compounds can be regarded as closer structural relatives to inorganic (oxide) perovskites, in the sense that they contain direct linkages of the octahedral sites via bridging oxygen atoms (of the oxalate groups). It is of note, therefore, that monoatomic cations as large as Cs⁺ can be incorporated into the perovskite-like A sites of this structure type, which is not feasible in traditional ABO₃ perovskites; indeed CsLi₃Ni(C₂O₄)₃ appears to exhibit the ‘mostly tightly bound’ 12-coordinate Cs⁺ ion in an oxide environment, according to a bond valence analysis.

Original language	English
Pages (from-to)	14461-14466
Number of pages	6
Journal	Dalton Transactions
Volume	48
Issue number	38
Early online date	6 Sept 2019
DOIs	https://doi.org/10.1039/c9dt03149a
Publication status	Published - 14 Oct 2019

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Copyright © 2019 The Author(s). This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1039/C9DT03149A
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@article{4c54002c2f0e441eabe6f25446785782,

title = "Perovzalates: a family of perovskite-related oxalates",

abstract = "A family of hybrid Perovskite-oxalates (“Perovzalates”) of general composition AILi3MII(C2O4)3 (A = K+, Rb+, Cs+; M = Fe2+, Co2+, Ni2+) are presented. All eight new compounds are isostructural with the previously reported examples NH4Li3Fe(C2O4)3 and KLi3Fe(C2O4)3, crystallising in the rhombohedral space group Rc, with a ∼11.3–11.6 {\AA}, c ∼14.8–15.2 {\AA}. In contrast to other families of “hybrid perovskites” such as the formates, these compounds can be regarded as closer structural relatives to inorganic (oxide) perovskites, in the sense that they contain direct linkages of the octahedral sites via bridging oxygen atoms (of the oxalate groups). It is of note, therefore, that monoatomic cations as large as Cs+ can be incorporated into the perovskite-like A sites of this structure type, which is not feasible in traditional ABO3 perovskites; indeed CsLi3Ni(C2O4)3 appears to exhibit the {\textquoteleft}mostly tightly bound{\textquoteright} 12-coordinate Cs+ ion in an oxide environment, according to a bond valence analysis.",

author = "Rebecca Clulow and Bradford, \{Alasdair J.\} and Lee, \{Stephen L.\} and Philip Lightfoot",

note = "Authors would like to thank the University of St Andrews (studentship to AJB) and the EPSRC (doctoral studentship to RC: DTG012 EP/K503162-1) for funding.",

year = "2019",

month = oct,

day = "14",

doi = "10.1039/c9dt03149a",

language = "English",

volume = "48",

pages = "14461--14466",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "38",

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TY - JOUR

T1 - Perovzalates

T2 - a family of perovskite-related oxalates

AU - Clulow, Rebecca

AU - Bradford, Alasdair J.

AU - Lee, Stephen L.

AU - Lightfoot, Philip

N1 - Authors would like to thank the University of St Andrews (studentship to AJB) and the EPSRC (doctoral studentship to RC: DTG012 EP/K503162-1) for funding.

PY - 2019/10/14

Y1 - 2019/10/14

N2 - A family of hybrid Perovskite-oxalates (“Perovzalates”) of general composition AILi3MII(C2O4)3 (A = K+, Rb+, Cs+; M = Fe2+, Co2+, Ni2+) are presented. All eight new compounds are isostructural with the previously reported examples NH4Li3Fe(C2O4)3 and KLi3Fe(C2O4)3, crystallising in the rhombohedral space group Rc, with a ∼11.3–11.6 Å, c ∼14.8–15.2 Å. In contrast to other families of “hybrid perovskites” such as the formates, these compounds can be regarded as closer structural relatives to inorganic (oxide) perovskites, in the sense that they contain direct linkages of the octahedral sites via bridging oxygen atoms (of the oxalate groups). It is of note, therefore, that monoatomic cations as large as Cs+ can be incorporated into the perovskite-like A sites of this structure type, which is not feasible in traditional ABO3 perovskites; indeed CsLi3Ni(C2O4)3 appears to exhibit the ‘mostly tightly bound’ 12-coordinate Cs+ ion in an oxide environment, according to a bond valence analysis.

AB - A family of hybrid Perovskite-oxalates (“Perovzalates”) of general composition AILi3MII(C2O4)3 (A = K+, Rb+, Cs+; M = Fe2+, Co2+, Ni2+) are presented. All eight new compounds are isostructural with the previously reported examples NH4Li3Fe(C2O4)3 and KLi3Fe(C2O4)3, crystallising in the rhombohedral space group Rc, with a ∼11.3–11.6 Å, c ∼14.8–15.2 Å. In contrast to other families of “hybrid perovskites” such as the formates, these compounds can be regarded as closer structural relatives to inorganic (oxide) perovskites, in the sense that they contain direct linkages of the octahedral sites via bridging oxygen atoms (of the oxalate groups). It is of note, therefore, that monoatomic cations as large as Cs+ can be incorporated into the perovskite-like A sites of this structure type, which is not feasible in traditional ABO3 perovskites; indeed CsLi3Ni(C2O4)3 appears to exhibit the ‘mostly tightly bound’ 12-coordinate Cs+ ion in an oxide environment, according to a bond valence analysis.

UR - https://www.scopus.com/pages/publications/85072790748

U2 - 10.1039/c9dt03149a

DO - 10.1039/c9dt03149a

M3 - Article

C2 - 31524905

AN - SCOPUS:85072790748

SN - 1477-9226

VL - 48

SP - 14461

EP - 14466

JO - Dalton Transactions

JF - Dalton Transactions

IS - 38

ER -

Perovzalates: a family of perovskite-related oxalates

Abstract

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