DataVXChemistry of MaterialsPaper
journal article·2020-04-14Open access

Topochemical Reduction of La2NiO3F2: The First Ni-Based Ruddlesden–Popper n = 1 T′-Type Structure and the Impact of Reduction on Magnetic Ordering

Kerstin Wissel, Ali Muhammad Malik, Sami Vasala, Sergi Plana-Ruiz, Ute Kolb, Peter R. Slater, Ivan da Silva, Lambert Alff, Jochen Rohrer, Oliver Clemens

Chemistry of Materials· Volume 32· Issue 7
Publisher pageOpen full text
Source abstract

Abstract

Within this study, we show that a broad range of reduced phases La2NiO3F2−Δ can be derived from Ruddlesden–Popper-type La2NiO3F2 using a reductive topochemical defluorination method based on reactions between the oxyfluoride and sodium hydride. The selective extraction of fluoride results in strong structural changes, and the nuclear and magnetic structures of the obtained phases have been determined. Due to the high anion content in La2NiO3F2, the formation of Ni+-containing compounds has been observed under reduction. For the first time, this has led to the formation of the highest reduced end member with a T′-type structure with an approximate composition of La2NiO3F in the n = 1 Ruddlesden–Popper-type series containing only Ni+ as the B-cation. This compound can be described as stacking of alternating (La/O2/La) fluorite-type layers with Lan–1(NiO2)n infinite layer structural blocks. The underlying reaction mechanism has been investigated by means of X-ray and neutron diffraction, elemental analysis, and magnetic measurements. Furthermore, to gain a deeper understanding of structural distortions, density functional theory-based calculations were performed, providing information about structural rearrangements upon defluorination and magnetic interactions. It is highlighted that the presence of even small amounts of d9-configured Ni+ cations leads to strong structural changes in La2NiO3F1.93, introducing long-range antiferromagnetic ordering between the adjacent perovskite building blocks by increasing the Ni–X–X–Ni super-superexchange interactions as compared to stoichiometric La2NiO3F2.
Source: openalex_inverted_index · Quality: baseline

Research context

Electronic materials

OpenAlex topics: Inorganic Fluorides and Related Compounds · Advanced Condensed Matter Physics · Inorganic Chemistry and Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Fachgebiet Materialdesign durch Synthese, Institut für Materialwissenschaft, Technical University of Darmstadt, Alarich-Weiss-Straße 2, 64287 Darmstadt, Germany

Fachgebiet Materialmodellierung, Institut für Materialwissenschaft, Technical University of Darmstadt, Otto-Berndt-Straße 3, 64287 Darmstadt, Germany

Fachgebiet Elektronenkristallographie, Institut für Angewandte Geowissenschaften, Technical University of Darmstadt, Schnittsphanstraße 9, 64287 Darmstadt, Germany

LENS-MIND, Departament d’Enginyeria Electrònica i Biomèdica, Universitat de Barcelona, Martí i Franquès 1, 08028 Barcelona, Catalonia

Institut für Anorganische Chemie und Analytische Chemie, Centre for High Resolution Electron Microscopy, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, 55128 Mainz, Germany

School of Chemistry, University of Birmingham, Birmingham B15 2TT, United Kingdom

ISIS Facility, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0QX, United Kingdom

Fachgebiet Dünne Schichten, Institut für Materialwissenschaft, Technical University of Darmstadt, Alarich-Weiss-Straße 2, 64287 Darmstadt, Germany

Institute for Nanotechnology, Karlsruhe Institute of Technology, Herrmann-von-Helmholtz-Platz 1, 73644 Eggenstein-Leopoldshafen, Germany

Funding

Engineering and Physical Sciences Research Council · Science and Technology Facilities Council · Deutsche Forschungsgemeinschaft

References (71)

Show source-provided references
1. 10.1002/adma.20100227410.1002/adma.201002274 ↗
2. 10.1016/b978-0-12-801639-8.00018-010.1016/b978-0-12-801639-8.00018-0 ↗
3. 10.1016/S1359-0286(98)80077-610.1016/S1359-0286(98)80077-6 ↗
4. 10.1016/j.jfluchem.2006.11.00810.1016/j.jfluchem.2006.11.008 ↗
5. 10.1515/revic-2013-000210.1515/revic-2013-0002 ↗
6. 10.1016/S0022-1139(02)00166-510.1016/S0022-1139(02)00166-5 ↗
7. 10.1039/b106574m10.1039/b106574m ↗
8. 10.1016/j.ssc.2005.03.00510.1016/j.ssc.2005.03.005 ↗
9. 10.1246/cl.13058110.1246/cl.130581 ↗
10. 10.1007/BF0130370110.1007/BF01303701 ↗
11. 10.1038/329423a010.1038/329423a0 ↗
12. 10.1016/0921-4534(90)90491-V10.1016/0921-4534(90)90491-V ↗
13. 10.1103/PhysRevLett.58.40510.1103/PhysRevLett.58.405 ↗
14. 10.1016/S0921-4534(88)80107-210.1016/S0921-4534(88)80107-2 ↗
15. 10.1016/0921-4534(91)91515-610.1016/0921-4534(91)91515-6 ↗
16. 10.1021/ic900912d10.1021/ic900912d ↗
17. 10.1103/PhysRevB.60.688810.1103/PhysRevB.60.6888 ↗
18. 10.1103/PhysRevB.59.790110.1103/PhysRevB.59.7901 ↗
19. 10.1103/PhysRevLett.104.20640310.1103/PhysRevLett.104.206403 ↗
20. 10.1103/PhysRevLett.102.04640510.1103/PhysRevLett.102.046405 ↗
21. 10.1039/F2983790118110.1039/F29837901181 ↗
22. 10.1021/ja991573i10.1021/ja991573i ↗
23. 10.1016/j.jssc.2005.01.02310.1016/j.jssc.2005.01.023 ↗
24. 10.1021/ic701480v10.1021/ic701480v ↗
25. 10.1021/ja063031o10.1021/ja063031o ↗
26. 10.1016/0022-4596(92)90061-Y10.1016/0022-4596(92)90061-Y ↗
27. 10.1006/jssc.1998.789210.1006/jssc.1998.7892 ↗
28. 10.1016/0022-4596(92)90102-210.1016/0022-4596(92)90102-2 ↗
29. 10.1021/acs.inorgchem.8b0066110.1021/acs.inorgchem.8b00661 ↗
30. 10.1039/C8TA01012A10.1039/C8TA01012A ↗
31. 10.1021/acs.inorgchem.9b0278310.1021/acs.inorgchem.9b02783 ↗
32. 10.1063/1.11575510.1063/1.115755 ↗
33. 10.1016/j.jmmm.2006.02.09410.1016/j.jmmm.2006.02.094 ↗
34. 10.1103/PhysRevLett.58.280210.1103/PhysRevLett.58.2802 ↗
35. 10.1021/acs.inorgchem.8b0050010.1021/acs.inorgchem.8b00500 ↗
36. Clemens O. · 2018
37. 10.1080/0032391049097056410.1080/00323910490970564 ↗
38. 10.1016/j.nima.2005.07.05310.1016/j.nima.2005.07.053 ↗
39. 10.1016/j.nima.2014.07.02910.1016/j.nima.2014.07.029 ↗
40. Diffrac.suite—User Manual TOPAS 5. Bruker AXS: Karlsruhe, Germany, 2014.
41. Coelho, A. A. TOPAS-Academic. http://www.topas-academic.net (accessed Oct 20, 2014).
42. 10.6028/jres.109.00210.6028/jres.109.002 ↗
43. 10.1016/j.ultramic.2006.10.00710.1016/j.ultramic.2006.10.007 ↗
44. 10.1016/j.ultramic.2020.11295110.1016/j.ultramic.2020.112951 ↗
45. 10.1016/0304-3991(94)90039-610.1016/0304-3991(94)90039-6 ↗
46. 10.1016/j.ultramic.2009.01.01110.1016/j.ultramic.2009.01.011 ↗
47. 10.1002/crat.20110003610.1002/crat.201100036 ↗
48. 10.1107/S160057671500113210.1107/S1600576715001132 ↗
49. 10.1515/zkri-2014-173710.1515/zkri-2014-1737 ↗
50. 10.1107/S205252061900753410.1107/S2052520619007534 ↗
51. 10.1103/PhysRevB.49.1425110.1103/PhysRevB.49.14251 ↗
52. 10.1016/0927-0256(96)00008-010.1016/0927-0256(96)00008-0 ↗
53. 10.1103/PhysRevB.59.175810.1103/PhysRevB.59.1758 ↗
54. 10.1103/PhysRevB.50.1795310.1103/PhysRevB.50.17953 ↗
55. 10.1103/PhysRevLett.77.386510.1103/PhysRevLett.77.3865 ↗
56. 10.1103/PhysRevB.57.150510.1103/PhysRevB.57.1505 ↗
57. 10.1103/PhysRevB.85.04511110.1103/PhysRevB.85.045111 ↗
58. 10.1103/PhysRevB.13.518810.1103/PhysRevB.13.5188 ↗
59. 10.1109/TCAPT.2004.82577510.1109/TCAPT.2004.825775 ↗
60. 10.1007/s10008-005-0687-110.1007/s10008-005-0687-1 ↗
61. Hancock, C. A. Anion Substitution in Perovskite Related Materials for Fuel Cell Applications. Ph.D. Thesis, University of Birmingham: Birmingham, 2012.
62. 10.1088/0953-8984/3/19/00210.1088/0953-8984/3/19/002 ↗
63. 10.1002/zaac.1975414011010.1002/zaac.19754140110 ↗
64. 10.1146/annurev-matsci-070214-02100810.1146/annurev-matsci-070214-021008 ↗
65. 10.1021/acs.inorgchem.6b0193810.1021/acs.inorgchem.6b01938 ↗
66. 10.1103/PhysRevB.44.504610.1103/PhysRevB.44.5046 ↗
67. 10.1039/c1jm13535j10.1039/c1jm13535j ↗
68. 10.1039/C4DT02485K10.1039/C4DT02485K ↗
69. 10.1002/open.20180010610.1002/open.201800106 ↗
70. 10.1039/C7TA09427B10.1039/C7TA09427B ↗
71. 10.1021/acs.chemmater.6b0507510.1021/acs.chemmater.6b05075 ↗