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Small Structural Variations Have Large Effects on the Assembly Properties and Spin State of Room Temperature High Spin Fe(II) Iminopyridine Cages.

Tabitha F MillerLauren R HollowayPhoebe P NyeYana LyonGregory J O BeranW Hill HarmanRyan R JulianRichard J Hooley
Published in: Inorganic chemistry (2018)
Small changes in steric bulk at the terminus of bis-iminopyridine ligands can effect large changes in the spin state of self-assembled Fe(II)-iminopyridine cage complexes. If the added bulk is properly matched with ligands that are either sufficiently flexible to allow twisted octahedral geometries at the Fe centers or can assemble with unusual mer configurations at the metals, room temperature high spin Fe(II) cages can be synthesized. These complexes maintain their high spin state in solution at low temperatures and have been characterized by X-ray crystallographic and computational methods. The high spin M2L3 meso-helicate and M4L6 cage complexes display longer N-Fe bond distances and larger interligand N-Fe-N bond angles than their diamagnetic counterparts, and these structural changes invert the ligand selectivity in narcissistic self-sorting and accelerate subcomponent exchange rates. The paramagnetic cages can be easily converted to diamagnetic cages by subcomponent exchange under mild conditions, and the intermediates of the exchange process can be visualized in situ by NMR analysis.
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