Design and Synthesis 2D Coordination Networks –

CrCl2(pyz)2 and Cr(OSO2CH3)2(pyz)2 (pyz= pyrazine)

Framework Magnets

Crystal Structure of CrCl2(pyz)2 Crystal structure of Cr(pyz)2(OSO2CH3)2

 Introduction
 Two dimensional (2D) material offer a plenty of exciting properties not seen in 3D materials that are
central to emergent molecular- scale electronics.

 2D materials that behave as both conductors and magnets can find applications in quantum magneto
electronics and sprintonics.

 We report the synthesis of CrCl2(pyrazine)2, an air-stable layered solid, by reaction of CrCl2 with
pyrazine (pyz).

 This compound displays a ferromagnetic order below 55K, reflecting the presence of strong magnetic
interactions.

 This compound reaches a conductivities of 32 mScm-1 at room temperature, which operates through
a 2D hopping-based transport mechanism.
 We suggest that the combination of redox-active ligands and reducing paramagnetic metal ions
represents a general approach towards tuneable 2D materials that consists of charge-neutral layers
and exhibit both long-range magnetic order and high electronic conductivity.

 With the aim to study the effect of the axial ligands on the magnetic and electronic properties of
analogous chromium/pyrazine 2D systems, we report herein the synthesis and characterization of
Cr(pyrazine)2(OSO2CH3)2 for which the chloride coligands of Cr(pyrazine)2Cl2 have been replaced
by methanesulfonate anions.
Results & Discussion
Conclusion
 A novel Cr/ pyrazine-based 2D coordination network has been synthesized by using Cr(OSO 2CH3)2,
a Precursor salt reported here for the first time. The structure of this coordination polymer, as
established from X-ray powder diffraction data, shows that this solid consists of neutral
Cr(pyrazine)2(OSO2CH3)2 layers containing an array of chromium metal ions bridged by bidentate
pyrazine ligands and coordinated to methanesulfonate anions in their apical positions.

 Supported by quantum chemical calculations, crystallographic, spectroscopic and magnetic

characterization demonstrate unequivocally the presence of high-spin Cr(II) centers which contrast
with the Cr(pyrazine)2Cl2 analogue which incorporates Cr(III) metal ions and a singly reduced
pyrazine scaffold, the redox process involving the oxidation of Cr(II) in Cr(III) and the reduction of
one pyrazine in Cr(pyrazine)2Cl2 is clearly disabled in Cr(pyrazine)2(OSO2CH3)2, likely due to the
change of the redox potential at the Cr site induced by the substitution of chloride by
methylsulfonate.
 This work clearly highlights that the activation of the redox process in these 2D pyrazine
coordination networks is the key parameter in the design of high TC magnets possessing high
electrical conductivity. We have shown how the redox-activity of a simple ligand, pyrazine, can be
used to enhance the electronic and magnetic communication in a layered material, the coordination
solid CrCl2(pyz)2.

 Layers of CrCl2(pyz)2 can be considered as a 2D version of the numerous molecular (0D) complexes
based on low-valent metal ions, which have shown strong ligand redox-activity and fascinating
electronic structures.2D coordination solids with improved properties can be designed using strongly
reducing transition metal ions in conjunction with organic ligands previously considered to be
wholly redox-inactive. The electrically neutral layers of CrCl 2(pyz)2 also provide the attractive
possibility for exfoliation and Nano structuring of this kind of material.
 We therefore believe that these results open up exciting new synthetic prospects for novel 2D
magnetic conductors derived from metal–organic coordination solids and capable of generating
spin-polarized currents in low-dimensional device.
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