Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Ionothermal Synthesis Enables Access to 3D Open Framework Manganese Phosphates Containing Extra-Large 18-Ring Channels
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). PORT Polish Center for Technology Development, Poland.ORCID iD: 0000-0002-1730-0304
Show others and affiliations
Number of Authors: 62019 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 31, no 18, p. 7329-7339Article in journal (Refereed) Published
Abstract [en]

An ionothermal synthesis study of transition metal phosphates using the ionic liquid 1-butyl-4-methylpyridinium hexafluorophosphate [C(4)mpy] [PF6] yielded four new, different open framework manganese compounds, that is, K2Mn3 (HPO4)(2)(PO3F)F-2 (1), (NH4)(2)Mn-3 (HPO4)(2) (PO3F)-F-2 (2), KMn3 (H2PO4)(HPO4)(2)F-2 (3), and (NH4)Mn-3(H2PO4)(PO3F)(2)F-2 (4). The obtained products not only feature new framework topologies unprecedented in the family of phosphates but also interesting properties as the transition metal gives rise to both luminescent (rendering them potential nonrare earth containing red emitting phosphors) and unconventional magnetic properties governed by geometric frustrations. Aside from the structural analysis (powder and single-crystal X-ray diffraction, infrared spectroscopy), a variety of characterization methods (photoluminescence spectroscopy and magnetic measurements) were applied to study the material's properties. Single crystal X-ray studies reveal that 1 (P2(1)/c with a = 5.501(1), b = 14.203(3), c = 16.905(4) angstrom, beta = 108.65(3)degrees, V = 1251.4 angstrom(3), and Z = 4) and 2 (P2(1)/c with a = 5.587(1), b = 14.507(3), c = 17.364(3) angstrom, beta = 108.75(3)degrees, V = 1332.6(5) angstrom(3), and Z = 4) feature S-shaped 18-ring channels along [100], which are formed by trimer-Mn3O9F2 chains parallel to [100] and interconnecting PO3 (OH) and PO3F tetrahedra. The structure of compounds 3 (C2/c with a = 20.307(4), b = 7.635(1), c = 7.834(2) angstrom, beta = 103.26(3)degrees, V = 1182.2(4) angstrom(3), and Z = 4) and 4 (C2/c with a = 20.402(4), b = 7.673(1), c = 7.845(2) angstrom, beta = 103.56(3)degrees, V = 1193.8(4) angstrom(3), and Z = 4) are characterized by layers, which are built of Mn3O8F4 octahedra trimers, with Kagome topology parallel to the be plane featuring 3,6-ring channels. The layers are stacked according to a sequence of AA(i) along the a axis. Taking into account the [P(2)O-3(OH)/P(2)O3F] tetrahedra, the Kagome layers are replenished to a Mn3O2 (HPO4)/Mn3O2 (PO3F) composition, which are interlinked by [P(1)O-2(OH)(2)] forming 10-ring channels parallel to [001]. Charge compensation of the macroanions is achieved by K+ (1 and 3) and (NH4)(+) (2 and 4) cations. At room temperature, compounds 1-4 demonstrate a reddish orange emission ascribed to the spin-forbidden T-4(1g)((4)G) -> (6)A(1g) (S-6) transition of the Mn2+ ions. Upon lowering the temperature to 77 K, the emission of each compound is red-shifted and becomes pure red. Compounds 1 and 2 contain spin trimers with a presumable doubled ground state. The intertrimer magnetic coupling is relatively weak, and small ferrimagnetic domains are possible in 1. The magnetic behavior of 3 and 4 can be considered as antiferromagnetic. This can be understood as their staircase Kagome lattices are distorted, meaning that the intrinsic geometrical frustration is lifted.

Place, publisher, year, edition, pages
2019. Vol. 31, no 18, p. 7329-7339
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-175053DOI: 10.1021/acs.chemmater.9b01935ISI: 000487859200025OAI: oai:DiVA.org:su-175053DiVA, id: diva2:1365821
Available from: 2019-10-25 Created: 2019-10-25 Last updated: 2019-10-25Bibliographically approved

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full text

Search in DiVA

By author/editor
Dorn, Katharina V.Wilk-Kozubek, MagdalenaSmetana, VolodymyrMudring, Anja-Verena
By organisation
Department of Materials and Environmental Chemistry (MMK)
In the same journal
Chemistry of Materials
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf