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Sciortino, Natasha
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article
Reversible guest binding in a non-porous FeII coordination polymer host toggles spin crossover
Abstract
<p>Formation of either a dimetallic compound or a 1D coordination polymer of adiponitrile adducts of [Fe(bpte)]<sup>2+</sup> (bpte=[1,2-bis(pyridin-2-ylmethyl)thio]ethane) can be controlled by the choice of counteranion. The iron(II) atoms of the bis(adiponitrile)-bridged dimeric complex [Fe<sub>2</sub>(bpte)<sub>2</sub>(μ<sub>2</sub>-(NC(CH<sub>2</sub>)<sub>4</sub>CN)<sub>2</sub>](SbF<sub>6</sub>)<sub>4</sub> (2) are low spin at room temperature, as are those in the polymeric adiponitrile-linked acetone solvate polymer {[Fe(bpte)(μ<sub>2</sub>-NC(CH<sub>2</sub>)<sub>4</sub>CN)](BPh<sub>4</sub>)<sub>2</sub> Me<sub>2</sub>CO} (3Me<sub>2</sub>CO). On heating 3Me<sub>2</sub>CO to 80°C, the acetone is abruptly removed with an accompanying purple to dull lavender colour change corresponding to a conversion to a high-spin compound. Cooling reveals that the desolvate 3 shows hysteretic and abrupt spin crossover (SCO) S=0虠S=2 behaviour centred at 205K. Non-porous 3 can reversibly absorb one equivalent of acetone per iron centre to regenerate the same crystalline phase of 3Me<sub>2</sub>CO concurrently reinstating a low-spin state.</p>