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Issue 43, 2015
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Structure and magnetic properties of the AB(HCO2)3 (A = Rb+ or Cs+, B = Mn2+, Co2+ or Ni2+) frameworks: probing the effect of size on the phase evolution of the ternary formates

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Abstract

This work reports the synthesis and structures of six new AB(HCO2)3 (A = Rb+ or Cs+ and B = Mn2+, Co2+ or Ni2+) frameworks containing the largest monoatomic cations on the A-site. RbMn(HCO2)3 is found to adopt a distorted perovskite framework with a 412·63 topology and a mixture of synanti and antianti ligands, while the remaining compounds adopt a chiral hexagonal structure with a 49·66 topology. The structures of these frameworks clarify the effect of ionic size on the formation of the five known architectures adopted by the AB(HCO2)3 frameworks, which have attracted attention as a new class of potential multiferroics, and in particular the chiral hexagonal structure within this. This also highlights the role of molecular A-site cations in stabilising the 49·66 topology for frameworks where such cations are too large or small to support this structure on the basis of size alone, possibly due to hydrogen bonding. The magnetic properties of the RbB(HCO2)3 and CsMn(HCO2)3 frameworks are also reported with the Rb+ compounds featuring weak ferromagnetic behaviour and the latter being purely antiferromagnetic. In conjunction with a comparison of the other isostructural AB(HCO2)3 frameworks we find that compounds adopting the 49·66 topology have much higher magnetic ordering temperatures than those with the RbMn(HCO2)3 structure, highlighting the importance of understanding the structure–property relationships of the ternary formates.

Graphical abstract: Structure and magnetic properties of the AB(HCO2)3 (A = Rb+ or Cs+, B = Mn2+, Co2+ or Ni2+) frameworks: probing the effect of size on the phase evolution of the ternary formates

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Supplementary files

Article information


Submitted
12 Aug 2015
Accepted
01 Oct 2015
First published
01 Oct 2015

CrystEngComm, 2015,17, 8319-8326
Article type
Paper
Author version available

Structure and magnetic properties of the AB(HCO2)3 (A = Rb+ or Cs+, B = Mn2+, Co2+ or Ni2+) frameworks: probing the effect of size on the phase evolution of the ternary formates

S. M. Bovill and P. J. Saines, CrystEngComm, 2015, 17, 8319
DOI: 10.1039/C5CE01628B

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