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A new chloro-bridged heterobimetallic Cu(II)Re(IV) chain of formula {Cu(pyim)(Him)2ReCl6}n·MeCN (1·MeCN) has been prepared and magnetostructurally characterised. Compound 1 is the first example of the [ReIVCl6]2− anion acting as a metalloligand towards a paramagnetic metal ion.

Graphical abstract: Metamagnetic behaviour in a new Cu(ii)Re(iv) chain based on the hexachlororhenate(iv) anion

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