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.
PY - 2015
Y1 - 2015
N2 - Formation of either a dimetallic compound or a 1 D 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 )4 CN)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} (3⋅Me2 CO). On heating 3⋅Me2CO 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↔S=2 behaviour centred at 205 K. Non-porous 3 can reversibly absorb one equivalent of acetone per iron centre to regenerate the same crystalline phase of 3⋅Me2CO concurrently reinstating a low-spin state.
AB - Formation of either a dimetallic compound or a 1 D 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 )4 CN)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} (3⋅Me2 CO). On heating 3⋅Me2CO 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↔S=2 behaviour centred at 205 K. Non-porous 3 can reversibly absorb one equivalent of acetone per iron centre to regenerate the same crystalline phase of 3⋅Me2CO concurrently reinstating a low-spin state.
U2 - 10.1002/chem.201502547
DO - 10.1002/chem.201502547
M3 - Journal article
C2 - 26394897
SN - 0947-6539
VL - 21
SP - 16066
EP - 16072
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 45
ER -