Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 34, 2018
Previous Article Next Article

Order in disorder: solution and solid-state studies of [M III2M II5] wheels (MIII = Cr, Al; MII = Ni, Zn)

Author affiliations

Abstract

A family of heterometallic Anderson-type ‘wheels’ of general formula [MIII2MII5(hmp)12](ClO4)4 (where MIII = Cr or Al and MII = Ni or Zn giving [Cr2Ni5] (1), [Cr2Zn5] (2), [Al2Ni5] (3) and [Al2Zn5] (4); hmpH = 2-pyridinemethanol) have been synthesised solvothermally. The metallic skeleton common to all structures describes a centred hexagon with the MIII sites disordered around the outer wheel. The structural disorder has been characterised via single crystal X-ray crystallography, 1–3D 1H and 13C solution-state NMR spectroscopy of the diamagnetic analogue (4), and solid-state 27Al MAS NMR spectroscopy of compounds (3) and (4). Alongside ESI mass spectrometry, these techniques show that structure is retained in solution, and that the disorder is present in both the solution and solid-state. Solid-state dc susceptibility and magnetisation measurements on (2) and (3) reveal the Cr–Cr and Ni–Ni exchange interactions to be JCr–Cr = −1 cm−1 and JNi–Ni,r = −5 cm−1, JNi–Ni,c = 10 cm−1. Fixing these values allows us to extract JCr–Ni,r = −1.2 cm−1, JCr–Ni,c = 2.6 cm−1 for (1), the exchange between adjacent Ni and Cr ions on the ring is antiferromagnetic and between Cr ions on the ring and the central Ni ion is ferromagnetic.

Graphical abstract: Order in disorder: solution and solid-state studies of [MIII2MII5] wheels (MIII = Cr, Al; MII = Ni, Zn)

Back to tab navigation

Supplementary files

Article information


Submitted
20 Feb 2018
Accepted
09 Mar 2018
First published
15 Mar 2018

This article is Open Access

Dalton Trans., 2018,47, 11834-11842
Article type
Paper

Order in disorder: solution and solid-state studies of [MIII2MII5] wheels (MIII = Cr, Al; MII = Ni, Zn)

H. W. L. Fraser, G. S. Nichol, D. Uhrín, U. G. Nielsen, M. Evangelisti, J. Schnack and E. K. Brechin, Dalton Trans., 2018, 47, 11834
DOI: 10.1039/C8DT00685G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements