Host Spin-Crossover Thermodynamics Indicate Guest Fit.
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Abstract
Spin-crossover (SCO) metal-organic cages capable of switching between high-spin and low-spin states have the potential to be used as magnetic sensors and switches. Variation of the donor strength of heterocyclic aldehyde subcomponents in imine-based ligands can tune the ligand field for a FeII center, which results in both homoleptic and heteroleptic cages with diverse SCO behaviors. The tetrahedral SCO cage built from 1-methyl-1H-imidazole-2-carbaldehyde is capable of encapsulating various guests, which stabilize different cage spin states depending on guest size. Conversely, the SCO tetrahedron exhibits different affinities for guests in different spin states, which is inferred to result from subtle structural differences of the cavity caused by the change in metal center spin state. Examination of SCO thermodynamics across a series of host-guest complexes enabled sensitive probing of guest fit to the host cavity, providing information complementary to binding-constant determination.
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Funder: Cambridge Trust; Id: http://dx.doi.org/10.13039/501100003343
Funder: Newnham College, University of Cambridge; Id: http://dx.doi.org/10.13039/501100000663
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1521-3773
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Engineering and Physical Sciences Research Council (EP/P027067/1)
EPSRC (EP/T031603/1)