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Title: Mixed X-Site Formate-Hypophosphite Hybrid Perovskites

Abstract

Following the recent discovery of a new family of hybrid ABX 3 perovskites where X=(H 2POO) - (hypophosphite), this paper reports a facile synthesis for mixed X-site formate perovskites of composition [GUA]Mn(HCOO) 3-x(H 2POO) x, with two crystallographically distinct, partially ordered intermediate phases with x=0.84 and 1.53, corresponding to ca. 30 and 50 mol % hypophosphite, respectively. These phases are characterised by single-crystal XRD and solid-state NMR spectroscopy, and their magnetic properties are reported.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [2]; ORCiD logo [5];  [6]; ORCiD logo [7]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy; National Univ. of Singapore (Singapore). Dept. of Materials Science and Engineering
  2. Univ. of Cambridge (United Kingdom). Dept. of Chemistry
  3. Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy; Agency for Science, Technology and Research (A*STAR) (Singapore). Inst. of Materials Research and Engineering
  4. Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy
  5. Leverhulme Research Centre for Functional Materials Design, The Materials Innovation Factory, Department of Chemistry, University of Liverpool, Liverpool L7 3NY UK
  6. Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy; Univ. of California, Los Angeles, CA (United States). David Geffen School of Medicine
  7. National Univ. of Singapore (Singapore). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, DC (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470673
Grant/Contract Number:  
SC0001294; SC0012583
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 24; Journal Issue: 44; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; energy storage (including batteries and capacitors); defects; charge transport; materials and chemistry by design; synthesis (novel materials); disordered structures; hybrid perovskite; metal-organic frameworks; paramagnetic NMR spectroscopy; perovskite phases

Citation Formats

Wu, Yue, Halat, David M., Wei, Fengxia, Binford, Trevor, Seymour, Ieuan D., Gaultois, Michael W., Shaker, Sammy, Wang, John, Grey, Clare P., and Cheetham, Anthony K. Mixed X-Site Formate-Hypophosphite Hybrid Perovskites. United States: N. p., 2018. Web. doi:10.1002/chem.201803061.
Wu, Yue, Halat, David M., Wei, Fengxia, Binford, Trevor, Seymour, Ieuan D., Gaultois, Michael W., Shaker, Sammy, Wang, John, Grey, Clare P., & Cheetham, Anthony K. Mixed X-Site Formate-Hypophosphite Hybrid Perovskites. United States. doi:10.1002/chem.201803061.
Wu, Yue, Halat, David M., Wei, Fengxia, Binford, Trevor, Seymour, Ieuan D., Gaultois, Michael W., Shaker, Sammy, Wang, John, Grey, Clare P., and Cheetham, Anthony K. Tue . "Mixed X-Site Formate-Hypophosphite Hybrid Perovskites". United States. doi:10.1002/chem.201803061. https://www.osti.gov/servlets/purl/1470673.
@article{osti_1470673,
title = {Mixed X-Site Formate-Hypophosphite Hybrid Perovskites},
author = {Wu, Yue and Halat, David M. and Wei, Fengxia and Binford, Trevor and Seymour, Ieuan D. and Gaultois, Michael W. and Shaker, Sammy and Wang, John and Grey, Clare P. and Cheetham, Anthony K.},
abstractNote = {Following the recent discovery of a new family of hybrid ABX3 perovskites where X=(H2POO)- (hypophosphite), this paper reports a facile synthesis for mixed X-site formate perovskites of composition [GUA]Mn(HCOO)3-x(H2POO)x, with two crystallographically distinct, partially ordered intermediate phases with x=0.84 and 1.53, corresponding to ca. 30 and 50 mol % hypophosphite, respectively. These phases are characterised by single-crystal XRD and solid-state NMR spectroscopy, and their magnetic properties are reported.},
doi = {10.1002/chem.201803061},
journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 44,
volume = 24,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
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Works referenced in this record:

Stability of Perovskite Solar Cells: A Prospective on the Substitution of the A Cation and X Anion
journal, November 2016

  • Wang, Ze; Shi, Zejiao; Li, Taotao
  • Angewandte Chemie International Edition, Vol. 56, Issue 5
  • DOI: 10.1002/anie.201603694

An anion substitution route to low loss colossal dielectric CaCu3Ti4O12
journal, February 2009

  • Smith, Andrew E.; Calvarese, T. G.; Sleight, A. W.
  • Journal of Solid State Chemistry, Vol. 182, Issue 2
  • DOI: 10.1016/j.jssc.2008.10.037

Defect-Assisted Photoinduced Halide Segregation in Mixed-Halide Perovskite Thin Films
journal, May 2017


The Hydride Anion in an Extended Transition Metal Oxide Array: LaSrCoO3H0.7
journal, March 2002


[Am]Mn(H 2 POO) 3 : A New Family of Hybrid Perovskites Based on the Hypophosphite Ligand
journal, November 2017

  • Wu, Yue; Shaker, Sammy; Brivio, Federico
  • Journal of the American Chemical Society, Vol. 139, Issue 47
  • DOI: 10.1021/jacs.7b09417

Stabilität von Perowskit-Solarzellen: Einfluss der Substitution von A-Kation und X-Anion
journal, November 2016


Coexistence of Magnetic and Electric Orderings in the Metal–Formate Frameworks of [NH 4 ][M(HCOO) 3 ]
journal, September 2011

  • Xu, Guan-Cheng; Zhang, Wen; Ma, Xiao-Ming
  • Journal of the American Chemical Society, Vol. 133, Issue 38
  • DOI: 10.1021/ja206891q

Polar nanoregions and diffuse scattering in the relaxor ferroelectric PbMg 1 / 3 Nb 2 / 3 O 3
journal, June 2012


Multiferroic Behavior Associated with an Order−Disorder Hydrogen Bonding Transition in Metal−Organic Frameworks (MOFs) with the Perovskite ABX 3 Architecture
journal, September 2009

  • Jain, Prashant; Ramachandran, Vasanth; Clark, Ronald J.
  • Journal of the American Chemical Society, Vol. 131, Issue 38
  • DOI: 10.1021/ja904156s

A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
journal, January 2016


Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound
journal, August 2010

  • Zhang, Wen; Cai, Ying; Xiong, Ren-Gen
  • Angewandte Chemie International Edition, Vol. 49, Issue 37
  • DOI: 10.1002/anie.201001208

An A-Site Mixed-Ammonium Solid Solution Perovskite Series of [(NH 2 NH 3 ) x (CH 3 NH 3 ) 1− x ][Mn(HCOO) 3 ] ( x =1.00-0.67)
journal, August 2015

  • Chen, Sa; Shang, Ran; Wang, Bing-Wu
  • Angewandte Chemie International Edition, Vol. 54, Issue 38
  • DOI: 10.1002/anie.201504396

Linking Local Environments and Hyperfine Shifts: A Combined Experimental and Theoretical 31 P and 7 Li Solid-State NMR Study of Paramagnetic Fe(III) Phosphates
journal, December 2010

  • Kim, Jongsik; Middlemiss, Derek S.; Chernova, Natasha A.
  • Journal of the American Chemical Society, Vol. 132, Issue 47
  • DOI: 10.1021/ja102678r

Perovskite-like Metal Formates with Weak Ferromagnetism and as Precursors to Amorphous Materials
journal, July 2004

  • Wang, Xin-Yi; Gan, Lin; Zhang, Shi-Wei
  • Inorganic Chemistry, Vol. 43, Issue 15
  • DOI: 10.1021/ic0498081

Chemically diverse and multifunctional hybrid organic–inorganic perovskites
journal, February 2017


Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016


An A-Site Mixed-Ammonium Solid Solution Perovskite Series of [(NH 2 NH 3 ) x (CH 3 NH 3 ) 1− x ][Mn(HCOO) 3 ] ( x =1.00-0.67)
journal, August 2015


Order−Disorder Antiferroelectric Phase Transition in a Hybrid Inorganic−Organic Framework with the Perovskite Architecture
journal, August 2008

  • Jain, Prashant; Dalal, Naresh S.; Toby, Brian H.
  • Journal of the American Chemical Society, Vol. 130, Issue 32
  • DOI: 10.1021/ja801952e

Phase Transitions and Coexistence of Magnetic and Electric Orders in the Methylhydrazinium Metal Formate Frameworks
journal, February 2017


Metal-Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [C(NH 2 ) 3 ][M II (HCOO) 3 ] (M=Mn, Fe, Co, Ni, Cu, and Zn; C(NH 2 ) 3 = Guanidinium)
journal, November 2009

  • Hu, Ke-Li; Kurmoo, Mohamedally; Wang, Zheming
  • Chemistry - A European Journal, Vol. 15, Issue 44
  • DOI: 10.1002/chem.200901605

Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound
journal, August 2010


Slush-like polar structures in single-crystal relaxors
journal, June 2017

  • Takenaka, Hiroyuki; Grinberg, Ilya; Liu, Shi
  • Nature, Vol. 546, Issue 7658
  • DOI: 10.1038/nature22068

Chemistry and applications of oxynitride perovskites
journal, January 2012

  • Fuertes, Amparo
  • Journal of Materials Chemistry, Vol. 22, Issue 8
  • DOI: 10.1039/c2jm13182j

    Works referencing / citing this record:

    Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound
    journal, August 2010


    An A-Site Mixed-Ammonium Solid Solution Perovskite Series of [(NH 2 NH 3 ) x (CH 3 NH 3 ) 1− x ][Mn(HCOO) 3 ] ( x =1.00-0.67)
    journal, August 2015


    Stabilität von Perowskit-Solarzellen: Einfluss der Substitution von A-Kation und X-Anion
    journal, November 2016


    Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound
    journal, August 2010

    • Zhang, Wen; Cai, Ying; Xiong, Ren-Gen
    • Angewandte Chemie International Edition, Vol. 49, Issue 37
    • DOI: 10.1002/anie.201001208

    An A-Site Mixed-Ammonium Solid Solution Perovskite Series of [(NH 2 NH 3 ) x (CH 3 NH 3 ) 1− x ][Mn(HCOO) 3 ] ( x =1.00-0.67)
    journal, August 2015

    • Chen, Sa; Shang, Ran; Wang, Bing-Wu
    • Angewandte Chemie International Edition, Vol. 54, Issue 38
    • DOI: 10.1002/anie.201504396

    Stability of Perovskite Solar Cells: A Prospective on the Substitution of the A Cation and X Anion
    journal, November 2016

    • Wang, Ze; Shi, Zejiao; Li, Taotao
    • Angewandte Chemie International Edition, Vol. 56, Issue 5
    • DOI: 10.1002/anie.201603694

    Metal-Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [C(NH 2 ) 3 ][M II (HCOO) 3 ] (M=Mn, Fe, Co, Ni, Cu, and Zn; C(NH 2 ) 3 = Guanidinium)
    journal, November 2009

    • Hu, Ke-Li; Kurmoo, Mohamedally; Wang, Zheming
    • Chemistry - A European Journal, Vol. 15, Issue 44
    • DOI: 10.1002/chem.200901605

    An anion substitution route to low loss colossal dielectric CaCu3Ti4O12
    journal, February 2009

    • Smith, Andrew E.; Calvarese, T. G.; Sleight, A. W.
    • Journal of Solid State Chemistry, Vol. 182, Issue 2
    • DOI: 10.1016/j.jssc.2008.10.037

    Phase Transitions and Coexistence of Magnetic and Electric Orders in the Methylhydrazinium Metal Formate Frameworks
    journal, February 2017


    Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
    journal, March 2016


    Defect-Assisted Photoinduced Halide Segregation in Mixed-Halide Perovskite Thin Films
    journal, May 2017


    Perovskite-like Metal Formates with Weak Ferromagnetism and as Precursors to Amorphous Materials
    journal, July 2004

    • Wang, Xin-Yi; Gan, Lin; Zhang, Shi-Wei
    • Inorganic Chemistry, Vol. 43, Issue 15
    • DOI: 10.1021/ic0498081

    Linking Local Environments and Hyperfine Shifts: A Combined Experimental and Theoretical 31 P and 7 Li Solid-State NMR Study of Paramagnetic Fe(III) Phosphates
    journal, December 2010

    • Kim, Jongsik; Middlemiss, Derek S.; Chernova, Natasha A.
    • Journal of the American Chemical Society, Vol. 132, Issue 47
    • DOI: 10.1021/ja102678r

    Coexistence of Magnetic and Electric Orderings in the Metal–Formate Frameworks of [NH 4 ][M(HCOO) 3 ]
    journal, September 2011

    • Xu, Guan-Cheng; Zhang, Wen; Ma, Xiao-Ming
    • Journal of the American Chemical Society, Vol. 133, Issue 38
    • DOI: 10.1021/ja206891q

    Order−Disorder Antiferroelectric Phase Transition in a Hybrid Inorganic−Organic Framework with the Perovskite Architecture
    journal, August 2008

    • Jain, Prashant; Dalal, Naresh S.; Toby, Brian H.
    • Journal of the American Chemical Society, Vol. 130, Issue 32
    • DOI: 10.1021/ja801952e

    Multiferroic Behavior Associated with an Order−Disorder Hydrogen Bonding Transition in Metal−Organic Frameworks (MOFs) with the Perovskite ABX 3 Architecture
    journal, September 2009

    • Jain, Prashant; Ramachandran, Vasanth; Clark, Ronald J.
    • Journal of the American Chemical Society, Vol. 131, Issue 38
    • DOI: 10.1021/ja904156s

    [Am]Mn(H 2 POO) 3 : A New Family of Hybrid Perovskites Based on the Hypophosphite Ligand
    journal, November 2017

    • Wu, Yue; Shaker, Sammy; Brivio, Federico
    • Journal of the American Chemical Society, Vol. 139, Issue 47
    • DOI: 10.1021/jacs.7b09417

    Chemically diverse and multifunctional hybrid organic–inorganic perovskites
    journal, February 2017


    Slush-like polar structures in single-crystal relaxors
    journal, June 2017

    • Takenaka, Hiroyuki; Grinberg, Ilya; Liu, Shi
    • Nature, Vol. 546, Issue 7658
    • DOI: 10.1038/nature22068

    Chemistry and applications of oxynitride perovskites
    journal, January 2012

    • Fuertes, Amparo
    • Journal of Materials Chemistry, Vol. 22, Issue 8
    • DOI: 10.1039/c2jm13182j

    The Hydride Anion in an Extended Transition Metal Oxide Array: LaSrCoO3H0.7
    journal, March 2002


    A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
    journal, January 2016