Mixed X-Site Formate-Hypophosphite Hybrid Perovskites
Abstract
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.
- Authors:
-
[1];
[2];
[5];
[7];
[2];
[1]
- Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy; National Univ. of Singapore (Singapore). Dept. of Materials Science and Engineering
- Univ. of Cambridge (United Kingdom). Dept. of Chemistry
- 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
- Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy
- Leverhulme Research Centre for Functional Materials Design, The Materials Innovation Factory, Department of Chemistry, University of Liverpool, Liverpool L7 3NY UK
- Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy; Univ. of California, Los Angeles, CA (United States). David Geffen School of Medicine
- 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)
- OSTI Identifier:
- 1470673
- Grant/Contract Number:
- SC0001294; SC0012583
- Resource Type:
- 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},
number = 44,
volume = 24,
place = {United States},
year = {2018},
month = {6}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 5 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
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
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
Defect-Assisted Photoinduced Halide Segregation in Mixed-Halide Perovskite Thin Films
journal, May 2017
- Barker, Alex J.; Sadhanala, Aditya; Deschler, Felix
- ACS Energy Letters, Vol. 2, Issue 6
The Hydride Anion in an Extended Transition Metal Oxide Array: LaSrCoO3H0.7
journal, March 2002
- Hayward, M.; Cussen, E.; Claridge, J.
- Science, Vol. 295, Issue 5561, p. 1882-1884
[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
Stabilität von Perowskit-Solarzellen: Einfluss der Substitution von A-Kation und X-Anion
journal, November 2016
- Wang, Ze; Shi, Zejiao; Li, Taotao
- Angewandte Chemie, Vol. 129, Issue 5
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
Polar nanoregions and diffuse scattering in the relaxor ferroelectric PbMg Nb O
journal, June 2012
- Paściak, M.; Welberry, T. R.; Kulda, J.
- Physical Review B, Vol. 85, Issue 22
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
A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
journal, January 2016
- McMeekin, D. P.; Sadoughi, G.; Rehman, W.
- Science, Vol. 351, Issue 6269
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
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
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
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
Chemically diverse and multifunctional hybrid organic–inorganic perovskites
journal, February 2017
- Li, Wei; Wang, Zheming; Deschler, Felix
- Nature Reviews Materials, Vol. 2, Issue 3
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016
- Saparov, Bayrammurad; Mitzi, David B.
- Chemical Reviews, Vol. 116, Issue 7
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, Vol. 127, Issue 38
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
Phase Transitions and Coexistence of Magnetic and Electric Orders in the Methylhydrazinium Metal Formate Frameworks
journal, February 2017
- Mączka, Mirosław; Gągor, Anna; Ptak, Maciej
- Chemistry of Materials, Vol. 29, Issue 5
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
Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound
journal, August 2010
- Zhang, Wen; Cai, Ying; Xiong, Ren-Gen
- Angewandte Chemie, Vol. 122, Issue 37
[NH 2 NH 3 ][M(HCOO) 3 ] (M = Mn 2+ , Zn 2+ , Co 2+ and Mg 2+ ): structural phase transitions, prominent dielectric anomalies and negative thermal expansion, and magnetic ordering
journal, January 2014
- Chen, Sa; Shang, Ran; Hu, Ke-Li
- Inorg. Chem. Front., Vol. 1, Issue 1
Slush-like polar structures in single-crystal relaxors
journal, June 2017
- Takenaka, Hiroyuki; Grinberg, Ilya; Liu, Shi
- Nature, Vol. 546, Issue 7658
Chemistry and applications of oxynitride perovskites
journal, January 2012
- Fuertes, Amparo
- Journal of Materials Chemistry, Vol. 22, Issue 8
Works referencing / citing this record:
Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound
journal, August 2010
- Zhang, Wen; Cai, Ying; Xiong, Ren-Gen
- Angewandte Chemie, Vol. 122, Issue 37
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, Vol. 127, Issue 38
Stabilität von Perowskit-Solarzellen: Einfluss der Substitution von A-Kation und X-Anion
journal, November 2016
- Wang, Ze; Shi, Zejiao; Li, Taotao
- Angewandte Chemie, Vol. 129, Issue 5
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
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
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
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
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
Phase Transitions and Coexistence of Magnetic and Electric Orders in the Methylhydrazinium Metal Formate Frameworks
journal, February 2017
- Mączka, Mirosław; Gągor, Anna; Ptak, Maciej
- Chemistry of Materials, Vol. 29, Issue 5
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016
- Saparov, Bayrammurad; Mitzi, David B.
- Chemical Reviews, Vol. 116, Issue 7
Defect-Assisted Photoinduced Halide Segregation in Mixed-Halide Perovskite Thin Films
journal, May 2017
- Barker, Alex J.; Sadhanala, Aditya; Deschler, Felix
- ACS Energy Letters, Vol. 2, Issue 6
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
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
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
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
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
[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
Chemically diverse and multifunctional hybrid organic–inorganic perovskites
journal, February 2017
- Li, Wei; Wang, Zheming; Deschler, Felix
- Nature Reviews Materials, Vol. 2, Issue 3
Slush-like polar structures in single-crystal relaxors
journal, June 2017
- Takenaka, Hiroyuki; Grinberg, Ilya; Liu, Shi
- Nature, Vol. 546, Issue 7658
Chemistry and applications of oxynitride perovskites
journal, January 2012
- Fuertes, Amparo
- Journal of Materials Chemistry, Vol. 22, Issue 8
[NH 2 NH 3 ][M(HCOO) 3 ] (M = Mn 2+ , Zn 2+ , Co 2+ and Mg 2+ ): structural phase transitions, prominent dielectric anomalies and negative thermal expansion, and magnetic ordering
journal, January 2014
- Chen, Sa; Shang, Ran; Hu, Ke-Li
- Inorg. Chem. Front., Vol. 1, Issue 1
Polar nanoregions and diffuse scattering in the relaxor ferroelectric PbMg Nb O
journal, June 2012
- Paściak, M.; Welberry, T. R.; Kulda, J.
- Physical Review B, Vol. 85, Issue 22
The Hydride Anion in an Extended Transition Metal Oxide Array: LaSrCoO3H0.7
journal, March 2002
- Hayward, M.; Cussen, E.; Claridge, J.
- Science, Vol. 295, Issue 5561, p. 1882-1884
A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
journal, January 2016
- McMeekin, D. P.; Sadoughi, G.; Rehman, W.
- Science, Vol. 351, Issue 6269
Tilts and shifts in molecular perovskites
journal, January 2020
- Boström, Hanna L. B.
- CrystEngComm, Vol. 22, Issue 5
Novel hypophosphite hybrid perovskites of [CH 3 NH 2 NH 2 ][Mn(H 2 POO) 3 ] and [CH 3 NH 2 NH 2 ][Mn(H 2 POO) 2.83 (HCOO) 0.17 ] exhibiting antiferromagnetic order and red photoluminescence
journal, January 2020
- Mączka, Mirosław; Gągor, Anna; Pikul, Adam
- RSC Advances, Vol. 10, Issue 32