AHMED, Manan; ZENERE, Katrina; SCIORTINO, Natasha; ARACHCHIGE, Kasun; TURNER, Gemma; CRUDDAS, Jace; HUA, Carol; PRICE, Jason; CLEGG, Jack; VALVERDE-MUÑOZ, Francisco; REAL, Jose; CHASTANET, Guillaume; MOGGACH, Stephen; KEPERT, Cameron; POWELL, Benjamin; NEVILLE, Suzanne

doi:10.1021/acs.inorgchem.2c00530

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AHMED, Manan
UNSW School of Chemistry [Sydney]

ZENERE, Katrina
School of Chemistry, The University of Sydney

SCIORTINO, Natasha
School of Chemistry, The University of Sydney

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Inorganic Chemistry. 2022-05-02, vol. 61, n° 17, p. 6641-6649

American Chemical Society

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We investigate the effects of a broad array of external stimuli on the structural, spin-crossover (SCO) properties and nature of the elastic interaction within the 2-D Hofmann framework material [Fe(cintrz)2Pd(CN)4]•guest (cintrz = N-cinnamalidene 4-amino-1,2,4-triazole; A•guest; guest = 3H2O, 2H2O & ∅). This framework exhibits a delicate balance between ferro-and antiferro-elastic interaction characters; we show that manipulation of the pore contents across guest = 3H2O, 2H2O and ∅ can be exploited to regulate this balance. In A•3H2O, dominant antiferroelastic interaction character between neighboring Fe II sites sees the low temperature persistence of the mixed spin-state species {HS-LS}, for {Fe1-Fe2} (HS = high spin, LS = low spin). Elastic interaction strain is responsible for stabilizing the {HS-LS} state and can be overcome by three mechanisms: (1) partial (2H2O) or complete (∅) guest removal, (2) irradiation via the reverse-LIESST effect ( = 830 nm; light-induced excited spin-state trapping) and (3) the application of external hydrostatic pressure. Combining experimental data with elastic models presents a clear interpretation that while guest molecules cause a negative chemical pressure, they also have consequences for the elastic interactions between metals beyond the simple chemical pressure picture typically proposed.< Réduire

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Regulation of Multistep Spin Crossover Across Multiple Stimuli in a 2-D Framework Material

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