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Issue 39, 2015
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Synthesis, crystal structure and magnetic properties of H2tppz[ReCl6] and [Cu(bpzm)2(μ-Cl)ReCl3(μ-ox)Cu(bpzm)2(μ-ox)ReCl3(μ-Cl)]n

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Abstract

Two new Re(IV) compounds of formulae H2tppz[ReCl6] (1) and [Cu(bpzm)2(μ-Cl)ReCl3(μ-ox)Cu(bpzm)2(μ-ox)ReCl3(μ-Cl)]n (2) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and bpzm = bis(pyrazolyl-1-yl)methane] have been prepared and their crystal structures determined by X-ray diffraction on single crystals. Compound 1 is a mononuclear species whose structure consists of octahedral hexachlororhenate(IV) anions and diprotonated H2tppz2+ cations which are arranged in the unit cell as alternating anionic and cationic layers, held together by electrostatic forces. The structure of 2 is made up of alternating [Cu(1)(bpzm)2]2+ and [(ox)ReCl3(μ-Cl)Cu(2)(bpzm)2(μ-Cl)ReCl3(ox)]2− entities interlinked by oxalate bridges to afford a neutral heterobimetallic chain. The oxalate group adopts the didentate (at Re)/monodentate (at Cu) bridging mode. The magnetic behavior of 1 and 2 has been investigated over the temperature range 1.9–295 K. 1 is a magnetically diluted Re(IV) complex, the relatively large value of the zero-field splitting of the ground level [D = −15.8(2) cm−1] accounting for the variation of χMT in the low temperature range. Weak intrachain ferromagnetic interactions between Re(IV) and Cu(II) through oxalate (J1 = +0.15 cm−1) and single chloro (J2 = +4.9 cm−1) bridges occur in 2 which are obscured by the large zero-field splitting of the Re(IV) ion (DRe = 42 cm−1). In addition, interchain antiferromagnetic interactions are also involved in 2 which are responsible for the metamagnetic behavior observed, the value of the critical dc magnetic field (Hc) being 20 kOe.

Graphical abstract: Synthesis, crystal structure and magnetic properties of H2tppz[ReCl6] and [Cu(bpzm)2(μ-Cl)ReCl3(μ-ox)Cu(bpzm)2(μ-ox)ReCl3(μ-Cl)]n

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Publication details

The article was received on 02 Jul 2015, accepted on 27 Aug 2015 and first published on 28 Aug 2015


Article type: Paper
DOI: 10.1039/C5DT02522B
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Citation: Dalton Trans., 2015,44, 17118-17128
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    Synthesis, crystal structure and magnetic properties of H2tppz[ReCl6] and [Cu(bpzm)2(μ-Cl)ReCl3(μ-ox)Cu(bpzm)2(μ-ox)ReCl3(μ-Cl)]n

    I. Gryca, J. Palion-Gazda, B. Machura, M. Penkala, R. Kruszyński, J. Cano, F. Lloret and M. Julve, Dalton Trans., 2015, 44, 17118
    DOI: 10.1039/C5DT02522B

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