Reversible guest binding in a non-porous Fe^II coordination polymer host toggles spin crossover

TY - JOUR

T1 - Reversible guest binding in a non-porous FeII coordination polymer host toggles spin crossover

AU - Lennartson, Anders

AU - Southon, Peter

AU - Sciortino, Natasha F.

AU - Kepert, Cameron J.

AU - Frandsen, Cathrine

AU - Mørup, Steen

AU - Piligkos, Stergios

AU - McKenzie, Christine J.

N1 - © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2015/11/1

Y1 - 2015/11/1

N2 - Formation of either a dimetallic compound or a 1D coordination polymer of adiponitrile adducts of [Fe(bpte)]2+ (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 [Fe2(bpte)2(μ2-(NC(CH2)4CN)2](SbF6)4 (2) are low spin at room temperature, as are those in the polymeric adiponitrile-linked acetone solvate polymer {[Fe(bpte)(μ2-NC(CH2)4CN)](BPh4)2 Me2CO} (3Me2CO). On heating 3Me2CO 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 3Me2CO concurrently reinstating a low-spin state.

AB - Formation of either a dimetallic compound or a 1D coordination polymer of adiponitrile adducts of [Fe(bpte)]2+ (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 [Fe2(bpte)2(μ2-(NC(CH2)4CN)2](SbF6)4 (2) are low spin at room temperature, as are those in the polymeric adiponitrile-linked acetone solvate polymer {[Fe(bpte)(μ2-NC(CH2)4CN)](BPh4)2 Me2CO} (3Me2CO). On heating 3Me2CO 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 3Me2CO concurrently reinstating a low-spin state.

U2 - 10.1002/chem.201502547

DO - 10.1002/chem.201502547

M3 - Journal article

C2 - 26394897

SN - 1521-3765

VL - 21

SP - 16066

EP - 16072

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

IS - 45

ER -