The University of Southampton
University of Southampton Institutional Repository

One-dimensional magnetism in new, layered structures: piperazine-linked copper and nickel oxalate chains

One-dimensional magnetism in new, layered structures: piperazine-linked copper and nickel oxalate chains
One-dimensional magnetism in new, layered structures: piperazine-linked copper and nickel oxalate chains
Two new coordination network materials with the composition M(pip)(ox) (pip = piperazine; ox = oxalate; M = Ni, Cu) have been synthesised under ambient and hydrothermal conditions. These compounds adopt related structures, both consisting of intersecting [M(pip)](infinity) and [M(ox)](infinity) chains, which result in layered structures. The nickel compound crystallises in P (1) over bar. The metal ions are octahedrally coordinated and are linked by symmetric chelating bridging oxalate ions. In contrast, the copper compound crystallises in the chiral space group P2(1)2(1)2(1). Here the copper atom displays square pyramidal coordination geometry and the oxalate ions bridge metals in an unsymmetric fashion resulting in a polar metal-oxalate chain structure. The magnetic behaviour is determined by the nature of the exchange-coupled net-work. Only the antiferromagnetic interaction mediated by the bridging oxalate group is significant and the compounds are well modelled as 1-D antiferromagnetically coupled chains. For the copper compound (S = 1/2) we determined J/k(B) to be -25.9 K, while the nickel compound (S = 1) shows a larger exchange coupling (J/k(B) = -42.2 K). In the nickel compound we see a significant deviation between the observed and calculated magnetic susceptibilities at the lowest experimental temperatures. This may be due either to the formation of a Haldane quantum antiferromagnetic ground state or to single-ion zero-field splitting effects.
magnetic properties, layered compounds, hydrothermal synthesis, coordination networks, directing organic amines, rystal-structure, x-ray, electronic-structure, binuclear complexes, peripheral ligands, bridgednetworks, open-framework, zinc oxalates, haldane-gap
1434-1948
1007-1013
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Ogilvie, Helen R.
667a68cc-7f86-47e6-a7fb-e9d3b7fdd488
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Price, Daniel J.
479ee5e3-2626-4abe-bffa-679d77ba5192
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Ogilvie, Helen R.
667a68cc-7f86-47e6-a7fb-e9d3b7fdd488
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Price, Daniel J.
479ee5e3-2626-4abe-bffa-679d77ba5192

Keene, Tony D., Ogilvie, Helen R., Hursthouse, Michael B. and Price, Daniel J. (2004) One-dimensional magnetism in new, layered structures: piperazine-linked copper and nickel oxalate chains. European Journal of Inorganic Chemistry, (5), 1007-1013. (doi:10.1002/ejic.200300592).

Record type: Article

Abstract

Two new coordination network materials with the composition M(pip)(ox) (pip = piperazine; ox = oxalate; M = Ni, Cu) have been synthesised under ambient and hydrothermal conditions. These compounds adopt related structures, both consisting of intersecting [M(pip)](infinity) and [M(ox)](infinity) chains, which result in layered structures. The nickel compound crystallises in P (1) over bar. The metal ions are octahedrally coordinated and are linked by symmetric chelating bridging oxalate ions. In contrast, the copper compound crystallises in the chiral space group P2(1)2(1)2(1). Here the copper atom displays square pyramidal coordination geometry and the oxalate ions bridge metals in an unsymmetric fashion resulting in a polar metal-oxalate chain structure. The magnetic behaviour is determined by the nature of the exchange-coupled net-work. Only the antiferromagnetic interaction mediated by the bridging oxalate group is significant and the compounds are well modelled as 1-D antiferromagnetically coupled chains. For the copper compound (S = 1/2) we determined J/k(B) to be -25.9 K, while the nickel compound (S = 1) shows a larger exchange coupling (J/k(B) = -42.2 K). In the nickel compound we see a significant deviation between the observed and calculated magnetic susceptibilities at the lowest experimental temperatures. This may be due either to the formation of a Haldane quantum antiferromagnetic ground state or to single-ion zero-field splitting effects.

This record has no associated files available for download.

More information

e-pub ahead of print date: 28 January 2004
Published date: March 2004
Keywords: magnetic properties, layered compounds, hydrothermal synthesis, coordination networks, directing organic amines, rystal-structure, x-ray, electronic-structure, binuclear complexes, peripheral ligands, bridgednetworks, open-framework, zinc oxalates, haldane-gap

Identifiers

Local EPrints ID: 20252
URI: http://eprints.soton.ac.uk/id/eprint/20252
ISSN: 1434-1948
PURE UUID: 2757e031-e1aa-445c-8ac5-ea7dcd96cf09
ORCID for Tony D. Keene: ORCID iD orcid.org/0000-0003-2297-4327

Catalogue record

Date deposited: 21 Feb 2006
Last modified: 15 Mar 2024 06:23

Export record

Altmetrics

Contributors

Author: Tony D. Keene ORCID iD
Author: Helen R. Ogilvie
Author: Daniel J. Price

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×