Activating a high-spin iron(<scp>ii</scp>) complex to thermal spin-crossover with an inert non-isomorphous molecular dopant

Halcrow, Malcolm A.; Vasili, Hari Babu; Pask, Christopher M.; Kulak, Alexander N.; Cespedes, Oscar

doi:10.1039/d4dt00443d

Dalton Trans.

2024

DOI: 10.1039/d4dt00443d

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Activating a high-spin iron(ii) complex to thermal spin-crossover with an inert non-isomorphous molecular dopant

Malcolm A. Halcrow,

Hari Babu Vasili,

Christopher M. Pask

et al.

Abstract: [Fe(bpp)2][ClO4]2 (bpp = 2,6-bis{pyrazol-1-yl}pyridine; monoclinic, C2/c) is high-spin between 5-300 K, and crystallises with a highly distorted molecular geometry that lies along the octahedral−trigonal prismatic distortion pathway. In contrast, [Ni(bpp)2][ClO4]2...

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Structural Consequences of Different Metal Compositions in the Doped Spin‐Crossover Crystals [Fe_zM_1−z(bpp)₂][BF₄]₂ (M=Ni, Zn; bpp=2,6‐Bis{Pyrazol‐1‐yl}Pyridine)

Pask,

Kulak,

Halcrow

2024

Eur J Inorg Chem

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Variable temperature crystallographic characterization of [FezZn1‒z(bpp)2][BF4]2 (bpp = 2,6‐bis{pyrazol‐1‐yl}pyridine; z = 0.88, 0.72 and 0.27) and [FezNi1‒z(bpp)2][BF4]2 (z = 0.83, 0.72 and 0.32) is presented. Comparison with previously published data confirms the isothermal unit cell volume change during spin‐crossover (ΔVSCO) behaves differently in the Zn‐ and Ni‐doped crystals. For the FeZn crystals, the relationship between ΔVSCO and z is continuous for z ≥ 0.3 but is steeper than expected, so ΔVSCO ≈ 0 for z = 0.27. In contrast ΔVSCO in the FeNi materials shows only a small variation between 0.83 ≥ z ≥ 0.46, before decreasing more strongly at higher dilution. ΔVSCO in each FeZn crystal is smaller than for its FeNi analogue with a similar composition. As well as the dopant ion ionic radius, the smaller ΔVSCO for the Zn‐doped materials reflects their T½ values, which are lower than for their FeNi counterparts. The contribution of T½ to this behavior is especially evident at high metal dilution.

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Structural Consequences of Different Metal Compositions in the Doped Spin‐Crossover Crystals [Fe_zM_1−z(bpp)₂][BF₄]₂ (M=Ni, Zn; bpp=2,6‐Bis{Pyrazol‐1‐yl}Pyridine)

Pask,

Kulak,

Halcrow

2024

Eur J Inorg Chem

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Mix and match – controlling the functionality of spin-crossover materials through solid solutions and molecular alloys

Halcrow

2024

Dalton Trans.

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Activating a high-spin iron(ii) complex to thermal spin-crossover with an inert non-isomorphous molecular dopant

Abstract: [Fe(bpp)2][ClO4]2 (bpp = 2,6-bis{pyrazol-1-yl}pyridine; monoclinic, C2/c) is high-spin between 5-300 K, and crystallises with a highly distorted molecular geometry that lies along the octahedral−trigonal prismatic distortion pathway. In contrast, [Ni(bpp)2][ClO4]2...

Cited by 2 publications

References 107 publications

Structural Consequences of Different Metal Compositions in the Doped Spin‐Crossover Crystals [Fe_zM_1−z(bpp)₂][BF₄]₂ (M=Ni, Zn; bpp=2,6‐Bis{Pyrazol‐1‐yl}Pyridine)

Structural Consequences of Different Metal Compositions in the Doped Spin‐Crossover Crystals [Fe_zM_1−z(bpp)₂][BF₄]₂ (M=Ni, Zn; bpp=2,6‐Bis{Pyrazol‐1‐yl}Pyridine)

Mix and match – controlling the functionality of spin-crossover materials through solid solutions and molecular alloys

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Activating a high-spin iron(ii) complex to thermal spin-crossover with an inert non-isomorphous molecular dopant

Abstract: [Fe(bpp)2][ClO4]2 (bpp = 2,6-bis{pyrazol-1-yl}pyridine; monoclinic, C2/c) is high-spin between 5-300 K, and crystallises with a highly distorted molecular geometry that lies along the octahedral−trigonal prismatic distortion pathway. In contrast, [Ni(bpp)2][ClO4]2...

Cited by 2 publications

References 107 publications

Structural Consequences of Different Metal Compositions in the Doped Spin‐Crossover Crystals [FezM1−z(bpp)2][BF4]2 (M=Ni, Zn; bpp=2,6‐Bis{Pyrazol‐1‐yl}Pyridine)

Structural Consequences of Different Metal Compositions in the Doped Spin‐Crossover Crystals [FezM1−z(bpp)2][BF4]2 (M=Ni, Zn; bpp=2,6‐Bis{Pyrazol‐1‐yl}Pyridine)

Mix and match – controlling the functionality of spin-crossover materials through solid solutions and molecular alloys

Contact Info

Product

Resources

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Structural Consequences of Different Metal Compositions in the Doped Spin‐Crossover Crystals [Fe_zM_1−z(bpp)₂][BF₄]₂ (M=Ni, Zn; bpp=2,6‐Bis{Pyrazol‐1‐yl}Pyridine)

Structural Consequences of Different Metal Compositions in the Doped Spin‐Crossover Crystals [Fe_zM_1−z(bpp)₂][BF₄]₂ (M=Ni, Zn; bpp=2,6‐Bis{Pyrazol‐1‐yl}Pyridine)