Issue 8, 2007
From the journal:

Dalton Transactions

The nano-scale molecule with the longest delocalized metal–metal bonds: linear heptacobalt(ii) metal string complexes [Co7(µ7-L)4X2]†‡

Wen-Zhen Wang,ab   Rayyat Huseyn Ismayilov,ab   Gene-Hsiang Lee,a   Isiah Po-Chun Liu,ab   Chen-Yu Yehc  and  Shie-Ming Peng*ab  

* Corresponding authors

a Department of Chemistry, National Taiwan University, Taipei, Taiwan, ROC

b Institute of Chemistry, Academia Sinica, Taipei, Taiwan, ROC
E-mail: smpeng@ntu.edu.tw

c Department of Chemistry, National Chung Hsing University, Taichung, Taiwan, ROC

Abstract

A new type of pyrazine-modulated oligo-α-pyridylamino ligands, N2-(pyrazin-2-yl)-N6-(6-(pyrazin-2-ylamino)pyridin-2-yl)pyridine-2,6-diamine (H3pzpz) (1) and N2-(pyrazin-2-yl)-N6-(6-(pyridin-2-ylamino)pyridin-2-yl)pyridine-2,6-diamine (H3tpz) (2), were synthesized and characterized by IR, 1H NMR and MS(FAB). Using 1 and 2, the linear heptacobalt(II) metal string complexes [Co7(µ7-L)4X2] (L = pzpz3−, X = Cl− (3), NCS− (4); L = tpz3−, X = Cl− (5), X = NCS− (6)) were synthesized and structurally characterized. The structures showed the shortest Co–Co distance (2.194 Å) and the longest Co chain (13.5 Å) obtained to date with direct Co–Co bonds. The Co–Co distances are in the range 2.194–2.309 Å. Electrochemical studies showed two reversible oxidations and one reversible reduction, while all the redox reactions of H3pzpz complexes, 3 and 4, occurred at higher potentials than H3tpz complexes, 5 and 6. The complexes 3–6 are fairly stable to oxidation. Temperature-dependent magnetic research on 3–6 revealed anomalous magnetic behavior with intermediate magnetic moment values between quartet and doublet states, and deviation from the Curie–Weiss law.

Graphical abstract: The nano-scale molecule with the longest delocalized metal–metal bonds: linear heptacobalt(ii) metal string complexes [Co7(µ7-L)4X2]

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Article information

DOI
https://doi.org/10.1039/B614661A
Article type
Paper
Submitted
05 Oct 2006
Accepted
11 Dec 2006
First published
09 Jan 2007

Dalton Trans., 2007, 830-839

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The nano-scale molecule with the longest delocalized metal–metal bonds: linear heptacobalt(II) metal string complexes [Co7(µ7-L)4X2]

W. Wang, R. H. Ismayilov, G. Lee, I. P. Liu, C. Yeh and S. Peng, Dalton Trans., 2007, 830 DOI: 10.1039/B614661A

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