title: Perturbation of spin crossover behavior by covalent post-synthetic modification of a porous metal-organic framework.
abstract: Covalent post-synthetic modification is a versatile method for gaining high-level synthetic control over functionality within porous metal-organic frameworks and for generating new materials not accessible through one-step framework syntheses. Here we apply this topotactic synthetic approach to a porous spin crossover framework and show through detailed comparison of the structures and properties of the as-synthesised and covalently modified phases that the modification reaction proceeds quantitatively by a thermally activated single-crystal-to-single-crystal transformation to yield a material with lowered spin-switching temperature, decreased lattice cooperativity, and altered color. Structure-function relationships to emerge from this comparison show that the approach provides a new route for tuning spin crossover through control over both outer-sphere and steric interactions.
authors: School of Chemistry, University of Sydney, Sydney, NSW 2006 (Australia).
authors: John E
authors: JE
authors: Clements
authors: Jason R
authors: JR
authors: Price
authors: Suzanne M
authors: SM
authors: Neville
authors: Cameron J
authors: CJ
authors: Kepert
keywords: host-guest systems; metal-organic frameworks; microporous materials; supramolecular chemistry