Unlocking room-temperature bistable spin transition at the nanoscale: the synthesis of core@shell [Fe(NH2trz)3(NO3)2]@SiO2 nanoparticles

Regueiro, A.; Martí-Carrascosa, M.; Torres-Cavanillas, R.; Coronado, E.

doi:10.1039/d4dt00911h

Dalton Trans.

2024

DOI: 10.1039/d4dt00911h

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Unlocking room-temperature bistable spin transition at the nanoscale: the synthesis of core@shell [Fe(NH₂trz)₃(NO₃)₂]@SiO₂ nanoparticles

A. Regueiro,

M. Martí-Carrascosa,

R. Torres-Cavanillas

et al.

Abstract: In this work, we address the synthesis of stable spin-crossover nanoparticles capable of undergoing a hysteretic spin transition at room temperature. For this purpose we use the reverse micelle protocol...

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Cited by 4 publications

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Size-Dependent Spin Crossover and Bond Flexibility in Metal–Organic Framework Nanoparticles

Davenport,

Marshall,

Nishiguchi

et al. 2024

J. Am. Chem. Soc.

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Size reduction offers a synthetic route to tunable phase change behavior. Preparing materials as nanoparticles causes drastic modulations to critical temperatures (T c), hysteresis widths, and the “sharpness” of first-order versus second-order phase transitions. A microscopic picture of the chemistry underlying this size dependence in phenomena ranging from melting to superconductivity remains debated. As a case study with broad implications, we report that size-dependent spin crossover (SCO) in nanocrystals of the metal–organic framework (MOF) Fe(1,2,3-triazolate)2 arises from metal-linker bonds becoming more labile in smaller particles. In comparison to the bulk material, differential scanning calorimetry indicates a ∼ 30–40% reduction in T c and ΔH in the smallest particles. Variable-temperature vibrational spectroscopy reveals a diminished long-range structural cooperativity, while X-ray diffraction evidence an over 3-fold increase in the thermal expansion coefficients. This “phonon softening” provides a molecular mechanism for designing size-dependent behavior in framework materials and for understanding phase changes in general.

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Size-Dependent Spin Crossover and Bond Flexibility in Metal–Organic Framework Nanoparticles

Davenport,

Marshall,

Nishiguchi

et al. 2024

J. Am. Chem. Soc.

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Design of stimuli-responsive transition metal dichalcogenides

Torres-Cavanillas,

Forment-Aliaga

2024

Commun Chem

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Stimuli-responsive systems are an emerging class of materials in fields as diverse as electronics, optoelectronics, cancer detection, drug delivery, or sensing. Especially focusing on nanomaterials, 2D transition metal dichalcogenides have recently attracted the scientific community's attention due to their remarkable intrinsic stimuli-responsive behaviour upon external stimuli such as pH, light, voltage, or certain pathogens. This significant response can be further enhanced by forming mixed-dimensional heterostructures and by molecular functionalization, capitalizing on chemistry to manipulate and boost their intrinsic stimuli-responsive properties. Furthermore, thanks to the endless possibilities of chemistry, a new class of smart materials based on the combination of stimuli-responsive molecular systems with transition metal dichalcogenides has recently been synthesized. In these materials, the physical properties of the 2D layers are reversibly modified by the switchable molecules, not only enhancing their stimuli-responsive behaviour but also providing memory to the hybrid. Therefore, this review explores the recent breakthroughs in the chemical design of smart transition metal dichalcogenides with built-in responsiveness.

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Spin crossover iron complexes with spin transition near room temperature based on nitrogen ligands containing aromatic rings: from molecular design to functional devices

Zhang,

Torres-Cavanillas,

Yan

et al. 2024

Chem. Soc. Rev.

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Unlocking room-temperature bistable spin transition at the nanoscale: the synthesis of core@shell [Fe(NH₂trz)₃(NO₃)₂]@SiO₂ nanoparticles

Abstract: In this work, we address the synthesis of stable spin-crossover nanoparticles capable of undergoing a hysteretic spin transition at room temperature. For this purpose we use the reverse micelle protocol...

Cited by 4 publications

References 38 publications

Size-Dependent Spin Crossover and Bond Flexibility in Metal–Organic Framework Nanoparticles

Size-Dependent Spin Crossover and Bond Flexibility in Metal–Organic Framework Nanoparticles

Design of stimuli-responsive transition metal dichalcogenides

Spin crossover iron complexes with spin transition near room temperature based on nitrogen ligands containing aromatic rings: from molecular design to functional devices

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