Four-step iron(ii) spin state cascade driven by antagonistic solid state interactions

A four-stepped cascade of Fe(ii) high spin (HS) to low spin (LS) states is demonstrated in a family of 2-D Hofmann materials, [Fe (saltrz) (M (CN) ) ]·8(H O) (M = Pd ( ), Pt ( ); saltrz = ( )-2-(((4 -1,2,4-triazol-4-yl)imino)methyl)phenol). Alongside the fully HS and LS Fe(ii) states, fractional spi...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2017-01, Vol.8 (1), p.701-707
Main Authors: Sciortino, Natasha F, Zenere, Katrina A, Corrigan, Maggie E, Halder, Gregory J, Chastanet, Guillaume, Létard, Jean-François, Kepert, Cameron J, Neville, Suzanne M
Format: Article
Language:English
Subjects:
Cascades
Chemical Sciences
Chemistry
Coordination chemistry
Crossovers
Flexibility
Lattices
Material chemistry
Networks
Patterning
Stabilization
Topology
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Summary:A four-stepped cascade of Fe(ii) high spin (HS) to low spin (LS) states is demonstrated in a family of 2-D Hofmann materials, [Fe (saltrz) (M (CN) ) ]·8(H O) (M = Pd ( ), Pt ( ); saltrz = ( )-2-(((4 -1,2,4-triazol-4-yl)imino)methyl)phenol). Alongside the fully HS and LS Fe(ii) states, fractional spin state stabilization occurs at HS/LS values of 5/6, 2/3, and 1/6. This unconventional spin state periodicity is driven by the presence of multiple spin crossover (SCO) active Fe(ii) sites which are in subtly distinct environments driven by a network of antagonistic host-host and host-guest interactions. Alternating long- and short-range magnetostructural ordering is achieved over the five distinct spin state ratios HS LS , HS LS , HS LS , HS LS , and HS LS owing to the flexibility of this 2-D interdigitated lattice topology interconnected by intermolecular interactions. A distinct wave-like spin state patterning is structurally evidenced for each intermediate phase.
ISSN:2041-6520
2041-6539
DOI:10.1039/c6sc03114e