Issue 16, 2010
From the journal:

Dalton Transactions

Probing the electronic communication of linear heptanickel and nonanickel string complexes by utilizing two redox-active [Ni2(napy)4]3+ moieties†

Shao-An Hua,a   Isiah Po-Chun Liu,‡ab   Hasan Hasanov,a   Gin-Chen Huang,a   Rayyat Huseyn Ismayilov,ab   Chien-Lan Chiu,c   Chen-Yu Yeh,c   Gene-Hsiang Leea  and  Shie-Ming Peng*ab  

* Corresponding authors

a Department of Chemistry, National Taiwan University, Taipei, Taiwan
E-mail: smpeng@ntu.edu.tw

b Institute of Chemistry, Academia Sinica, Taipei, Taiwan

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

Abstract

Two extended nickel string complexes, [Ni7(bnapy)4Cl2](Cl)2 (2) and [Ni9(bnapya)4Cl2](PF6)2 (3) (bnapy2− = 2,6-bis(1,8-naphthyridylamido)pyridine and bnapya3- = bis(6-(1,8-naphthyridylamido)pyridyl)amido), which possess two redox-active [Ni2(napy)4]3+ units, were synthesized and characterized. The electronic communication between the two redox-active units in both complexes can be investigated not only by magnetic measurements but also by analyzing the difference between two consecutive one-electron oxidation peaks (ΔE1/2) of 2 and 3. The antiferromagnetic coupling between the two [Ni2(napy)4]3+ fragments become weaker as the metal frameworks are elongated (J = −13.21 and −1.48 cm−1 for 2 and 3, respectively). Moreover, the ΔE1/2 values of 2 and 3 are 110 and 84 mV, respectively, which are smaller than that (300 mV) of their pentanickel analogue [Ni5(bna)4(Cl)2](PF6)2 (bna− = bisnaphthyridylamido) (1). These ΔE1/2 values indicate that the electronic communication decreases with increasing number of inner diamagnetic nickel ions in nickel string complexes.

Graphical abstract: Probing the electronic communication of linear heptanickel and nonanickel string complexes by utilizing two redox-active [Ni2(napy)4]3+ moieties

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Article information

DOI
https://doi.org/10.1039/B923125K
Article type
Paper
Submitted
04 Nov 2009
Accepted
16 Dec 2009
First published
28 Jan 2010

Dalton Trans., 2010,39, 3890-3896

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Probing the electronic communication of linear heptanickel and nonanickel string complexes by utilizing two redox-active [Ni2(napy)4]3+ moieties

S. Hua, I. P. Liu, H. Hasanov, G. Huang, R. H. Ismayilov, C. Chiu, C. Yeh, G. Lee and S. Peng, Dalton Trans., 2010, 39, 3890 DOI: 10.1039/B923125K

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