Issue 33, 2009
From the journal:

Dalton Transactions

Self-assembly of mixed-valence Co(ii/iii) and Ni(ii) clusters: azide-bridged 1D single chain coordination polymers comprised of tetranuclear units, tetranuclear Co(ii/iii) complexes, ferromagnetically coupled azide-bridged tetranuclear, and hexanuclear Ni(ii) complexes: synthesis, structural, and magnetic properties†

Santokh S. Tandon,*a   Scott D. Bunge,b   Robert Rakosi,b   Zhiqiang Xuc  and  Laurence K. Thompson*d  

* Corresponding authors

a Department of Chemistry, Kent State University Salem, Salem, OH, USA
E-mail: standon@kent.edu
Fax: +1-330-337-4122
Tel: +1-330-337-4235

b Department of Chemistry, Kent State University, Kent, OH, USA
E-mail: sbunge@kent.edu
Fax: +1-330-672-3816-
Tel: +1-330-672-9445

c SKC PowerTech, Inc. 850 Clark Drive, Mt. Olive, NJ, USA

d Department of Chemistry, Memorial University, St. John's, Newfoundland, Canada
E-mail: lthomp@mun.ca.
Fax: +1-709-737-3702
Tel: +1-709-737-8750

Abstract

One-pot reactions between 2,6-diformyl-4-methylphenol (DFMP) and 2-aminoethanol (AE) in the presence of cobalt(II) salts [Co(ClO4)2, CoCl2, Co(CH3CO2)2, Co(NO3)2] and sodium azide result in the self-assembly of novel one-dimensional single chain mixed-valence cobalt coordination polymers {[Co2IICo2III (HL)2(OCH3)2(N3)3]ClO4·5H2O·CH3OH}n (1), {[Co2IICo2III (HL)2(OCH3)2(N3)3]Cl·H2O}n (2) in which tetra-cobalt cationic units are bridged by symmetrical 1,3-azides, forming single chains; mixed valence neutral tetranuclear clusters [Co2IICo2III (HL)2(OCH3)2(N3)4]CH3OH·2H2O (3), [Co2IICo2III(HL)2(OCH3)2(N3)2(CH3CO2)2]·2CH3OH·2H2O (4), and the cationic cluster [Co2II Co2III (HL)2(OCH3)2(CH3OH)2(N3)2](NO3)2 (5). In all these reactions, H3L, the potentially pentadentate (N2O3), trianionic double Schiff base ligand 2,6-bis[(2-hydroxy-ethylimino)-methyl]-4-methylphenol is formed. The reaction between DFMP and AE in the presence of nickel(II) salts and sodium azide in methanol–water mixture results in the self-assembly of ferromagnetically coupled hexanuclear complexes [Ni6(H2L)2(HL-1)2(H2O)2(N3)6](ClO4)2·2CH3OH (6), and [Ni6(H2L)2(HL-1)2(CH3OH)2(N3)6](BF4)2 (7), involving double (H3L) and single (H2L-1) Schiff base ligands, and a neutral tetranuclear complex [Ni4(H2L)2(OCH3)2(CH3CO2)2(N3)2] (8) with only double Schiff-base (H3L). In these complexes, the nature of the anion and the reaction conditions seem to play an important role in directing the formation of tetranuclear, hexanuclear or polymeric clusters. All complexes involve divacant double cubane-type cores containing three to four different types of bridging ligands (phenoxy, azido, methoxy/alkoxy, and acetate). Variable temperature magnetic properties of these spin coupled clusters have been investigated and magneto-structural correlations have been established.

Graphical abstract: Self-assembly of mixed-valence Co(ii/iii) and Ni(ii) clusters: azide-bridged 1D single chain coordination polymers comprised of tetranuclear units, tetranuclear Co(ii/iii) complexes, ferromagnetically coupled azide-bridged tetranuclear, and hexanuclear Ni(ii) complexes: synthesis, structural, and magnetic properties

About
Cited by
Related
Download options Please wait...

Supplementary files

Additions and corrections

Article information

DOI
https://doi.org/10.1039/B903617B
Article type
Paper
Submitted
20 Feb 2009
Accepted
15 May 2009
First published
08 Jul 2009

Dalton Trans., 2009, 6536-6551

Permissions

Request permissions

Self-assembly of mixed-valence Co(II/III) and Ni(II) clusters: azide-bridged 1D single chain coordination polymers comprised of tetranuclear units, tetranuclear Co(II/III) complexes, ferromagnetically coupled azide-bridged tetranuclear, and hexanuclear Ni(II) complexes: synthesis, structural, and magnetic properties

S. S. Tandon, S. D. Bunge, R. Rakosi, Z. Xu and L. K. Thompson, Dalton Trans., 2009, 6536 DOI: 10.1039/B903617B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements