Issue 7, 2011
From the journal:

Dalton Transactions

π–π Stacking and ferromagnetic coupling mechanism on a binuclear Cu(ii) complex†

Yan-Hui Chi,a   Li Yu,a   Jing-Min Shi,*a   Yi-Quan Zhang,*b   Tai-Qiu Hu,a   Gui-Qiu Zhang,a   Wei Shic  and  Peng Chengc  

* Corresponding authors

a College of Chemistry, Chemical Engineering and Materials Science, Key Laboratory of Molecular and Nano Probes, Engineering Research Center of Pesticide and Medicine Intermediate Clean Production, Ministry of Education, Shandong Provincial Key Laboratory of Clean Production of Fine Chemicals, Shandong Normal University, Jinan, P. R. China
E-mail: shijingmin1955@yahoo.com.cn
Fax: 86-531-86180017
Tel: 86-531-86188367

b School of Physical Science and Technology, Nanjing Normal University, Nanjing, P. R. China
E-mail: zhangyiquan@njnu.edu.cn
Fax: 86-531-86180017
Tel: 86-531-86188367

c Department of Chemistry, Nankai University, Tianjin, P. R. China

Abstract

The ferromagnetic couplings were observed in an unpublished crystal that consists of binuclear copper(II) complexes, namely, [Cu2(μ1,3-SCN)2(PhenOH)(OCH3)2(HOCH3)2] (PhenOH = 2-hydroxy-1,10-phenanthroline), and in the binuclear complex Cu(II) ion assumes a distorted octahedral geometry and thiocyanate anion functions as a μ1,3-SCN− equatorial–axial (EA) bridging ligand. The analysis for the crystal structure indicates that there are three types of magnetic coupling pathways, in which two pathways involve π–π stacking between the adjacent complexes and the third one is the μ1,3-SCN− bridged pathway. The fitting for the data of the variable-temperature magnetic susceptibilities shows that there is a ferromagnetic coupling between adjacent Cu(II) ions with J = 50.02 cm−1. Theoretical calculations reveal that the two types of π–π stacking resulted in ferromagnetic couplings with J = 4.16 cm−1 and J = 2.75 cm−1, respectively, and the bridged thiocyanate anions pathway led to a weaker ferromagnetic interaction with J = 0.88 cm−1. The theoretical calculations also indicate that the ferromagnetic coupling sign from the two types of π–π stacking does not accord with McConnell I spin-polarization mechanism. The analysis for the Wiberg bond indexes that originate from the π–π stacking atoms indicates that the Wiberg bond indexes are relevant to the associated magnetic coupling magnitude and the Wiberg bond index is one of the key factors that dominates the associated magnetic coupling magnitude.

Graphical abstract: π–π Stacking and ferromagnetic coupling mechanism on a binuclear Cu(ii) complex

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Article information

DOI
https://doi.org/10.1039/C0DT01127D
Article type
Paper
Submitted
29 Aug 2010
Accepted
18 Nov 2010
First published
07 Jan 2011

Dalton Trans., 2011,40, 1453-1462

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π–π Stacking and ferromagnetic coupling mechanism on a binuclear Cu(II) complex

Y. Chi, L. Yu, J. Shi, Y. Zhang, T. Hu, G. Zhang, W. Shi and P. Cheng, Dalton Trans., 2011, 40, 1453 DOI: 10.1039/C0DT01127D

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