Hybrid Layered Double Perovskite Halides of Transition Metals

Pratap Vishnoi; Julia L. Zuo; Xiaotong Li; Devesh Chandra Binwal; Kira E. Wyckoff; Lingling Mao; Linus Kautzsch; Guang Wu; Stephen D. Wilson; Mercouri G. Kanatzidis; Ram Seshadri; Anthony K. Cheetham

doi:10.1021/jacs.1c12760

Hybrid Layered Double Perovskite Halides of Transition Metals

Pratap Vishnoi, Julia L. Zuo, Xiaotong Li, Devesh Chandra Binwal, Kira E. Wyckoff, Lingling Mao, Linus Kautzsch, Guang Wu, Stephen D. Wilson, Mercouri G. Kanatzidis, Ram Seshadri^*, Anthony K. Cheetham

^*Corresponding author for this work

Chemistry

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

13 Scopus citations

Abstract

Hybrid layered double perovskite (HLDP) halides comprise hexacoordinated 1+ and 3+ metals in the octahedral sites within a perovskite layer and organic amine cations between the layers. Progress on such materials has hitherto been limited to compounds containing main group 3+ ions isoelectronic with Pb^II(such as Sb^IIIand Bi^III). Here, we report eight HLDP halides from the A₂M^IM^IIIX₈family, where A = para-phenylenediammonium (PPDA), 1,4-butanediammonium (1,4-BDA), or 1,3-propanediammonium (1,3-PDA); M^I= Cu or Ag; M^III= Ru or Mo; X = Cl or Br. The optical band gaps, which lie in the range 1.55 to 2.05 eV, are tunable according to the layer composition, but are largely independent of the spacer. Magnetic measurements carried out for (PPDA)₂Ag^IRu^IIICl₈and (PPDA)₂Ag^IMo^IIICl₈show no obvious evidence of a magnetic ordering transition. While the t_2g³Mo^IIIcompound displays Curie-Weiss behavior for a spin-only d³ion, the t_2g⁵Ru^IIIcompound displays marked deviations from the Kotani theory.

Original language	English (US)
Pages (from-to)	6661-6666
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	144
Issue number	15
DOIs	https://doi.org/10.1021/jacs.1c12760
State	Published - Apr 20 2022

ASJC Scopus subject areas

Chemistry(all)
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.1c12760

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@article{c1b452dc71c34df08a313f2ab5199ba1,

title = "Hybrid Layered Double Perovskite Halides of Transition Metals",

abstract = "Hybrid layered double perovskite (HLDP) halides comprise hexacoordinated 1+ and 3+ metals in the octahedral sites within a perovskite layer and organic amine cations between the layers. Progress on such materials has hitherto been limited to compounds containing main group 3+ ions isoelectronic with PbII(such as SbIIIand BiIII). Here, we report eight HLDP halides from the A2MIMIIIX8family, where A = para-phenylenediammonium (PPDA), 1,4-butanediammonium (1,4-BDA), or 1,3-propanediammonium (1,3-PDA); MI= Cu or Ag; MIII= Ru or Mo; X = Cl or Br. The optical band gaps, which lie in the range 1.55 to 2.05 eV, are tunable according to the layer composition, but are largely independent of the spacer. Magnetic measurements carried out for (PPDA)2AgIRuIIICl8and (PPDA)2AgIMoIIICl8show no obvious evidence of a magnetic ordering transition. While the t2g3MoIIIcompound displays Curie-Weiss behavior for a spin-only d3ion, the t2g5RuIIIcompound displays marked deviations from the Kotani theory.",

author = "Pratap Vishnoi and Zuo, {Julia L.} and Xiaotong Li and Binwal, {Devesh Chandra} and Wyckoff, {Kira E.} and Lingling Mao and Linus Kautzsch and Guang Wu and Wilson, {Stephen D.} and Kanatzidis, {Mercouri G.} and Ram Seshadri and Cheetham, {Anthony K.}",

note = "Funding Information: This work was supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant No. SC0012541. P.V. thanks the Department of Science & Technology (DST) of Govt. of India for the Overseas Postdoctoral Visiting Fellowship (Award No. JNC/AO/A.0610-1(3)/2018-03), the Science & Engineering Research Board (SERB) of the Govt. of India for the Ramanujan Fellowship (Award No. RJF/2020/000106), and the Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) Bangalore for the financial support and the research infrastructure. We acknowledge the shared facility of the Materials Research Science and Engineering Center (MRSEC) at the UC Santa Barbara under the National Science Foundation (NSF) Grant Number DMR 1720256. J.L.Z. also acknowledges the support of the NSF Graduate Research Fellowship Program under Grant No. 1650114. A.K.C. thanks the Ras al Khaimah Centre for Advanced Materials for financial support. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

month = apr,

day = "20",

doi = "10.1021/jacs.1c12760",

language = "English (US)",

volume = "144",

pages = "6661--6666",

journal = "Journal of the American Chemical Society",

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TY - JOUR

T1 - Hybrid Layered Double Perovskite Halides of Transition Metals

AU - Vishnoi, Pratap

AU - Zuo, Julia L.

AU - Li, Xiaotong

AU - Binwal, Devesh Chandra

AU - Wyckoff, Kira E.

AU - Mao, Lingling

AU - Kautzsch, Linus

AU - Wu, Guang

AU - Wilson, Stephen D.

AU - Kanatzidis, Mercouri G.

AU - Seshadri, Ram

AU - Cheetham, Anthony K.

N1 - Funding Information: This work was supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant No. SC0012541. P.V. thanks the Department of Science & Technology (DST) of Govt. of India for the Overseas Postdoctoral Visiting Fellowship (Award No. JNC/AO/A.0610-1(3)/2018-03), the Science & Engineering Research Board (SERB) of the Govt. of India for the Ramanujan Fellowship (Award No. RJF/2020/000106), and the Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) Bangalore for the financial support and the research infrastructure. We acknowledge the shared facility of the Materials Research Science and Engineering Center (MRSEC) at the UC Santa Barbara under the National Science Foundation (NSF) Grant Number DMR 1720256. J.L.Z. also acknowledges the support of the NSF Graduate Research Fellowship Program under Grant No. 1650114. A.K.C. thanks the Ras al Khaimah Centre for Advanced Materials for financial support. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/4/20

Y1 - 2022/4/20

N2 - Hybrid layered double perovskite (HLDP) halides comprise hexacoordinated 1+ and 3+ metals in the octahedral sites within a perovskite layer and organic amine cations between the layers. Progress on such materials has hitherto been limited to compounds containing main group 3+ ions isoelectronic with PbII(such as SbIIIand BiIII). Here, we report eight HLDP halides from the A2MIMIIIX8family, where A = para-phenylenediammonium (PPDA), 1,4-butanediammonium (1,4-BDA), or 1,3-propanediammonium (1,3-PDA); MI= Cu or Ag; MIII= Ru or Mo; X = Cl or Br. The optical band gaps, which lie in the range 1.55 to 2.05 eV, are tunable according to the layer composition, but are largely independent of the spacer. Magnetic measurements carried out for (PPDA)2AgIRuIIICl8and (PPDA)2AgIMoIIICl8show no obvious evidence of a magnetic ordering transition. While the t2g3MoIIIcompound displays Curie-Weiss behavior for a spin-only d3ion, the t2g5RuIIIcompound displays marked deviations from the Kotani theory.

AB - Hybrid layered double perovskite (HLDP) halides comprise hexacoordinated 1+ and 3+ metals in the octahedral sites within a perovskite layer and organic amine cations between the layers. Progress on such materials has hitherto been limited to compounds containing main group 3+ ions isoelectronic with PbII(such as SbIIIand BiIII). Here, we report eight HLDP halides from the A2MIMIIIX8family, where A = para-phenylenediammonium (PPDA), 1,4-butanediammonium (1,4-BDA), or 1,3-propanediammonium (1,3-PDA); MI= Cu or Ag; MIII= Ru or Mo; X = Cl or Br. The optical band gaps, which lie in the range 1.55 to 2.05 eV, are tunable according to the layer composition, but are largely independent of the spacer. Magnetic measurements carried out for (PPDA)2AgIRuIIICl8and (PPDA)2AgIMoIIICl8show no obvious evidence of a magnetic ordering transition. While the t2g3MoIIIcompound displays Curie-Weiss behavior for a spin-only d3ion, the t2g5RuIIIcompound displays marked deviations from the Kotani theory.

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DO - 10.1021/jacs.1c12760

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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Hybrid Layered Double Perovskite Halides of Transition Metals

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CCDC 2122538: Experimental Crystal Structure Determination

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Hybrid Layered Double Perovskite Halides of Transition Metals

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CCDC 2122538: Experimental Crystal Structure Determination

CCDC 2122539: Experimental Crystal Structure Determination

CCDC 2122536: Experimental Crystal Structure Determination

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