AFM Imaging of Molecular Spin‐State Changes through Quantitative Thermomechanical Measurements

Hernández, Edna M.; Quintero, Carlos M.; Kraieva, Olena; Thibault, Christophe; Bergaud, Christian; Salmon, Lionel; Molnár, Gábor; Bousseksou, Azzedine

doi:10.1002/adma.201305539

Cited by 28 publications

(24 citation statements)

References 35 publications

(57 reference statements)

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“…In the HS state, the average phase angle shift is very similar to that in the LS state (14.4° vs. 14.9°) at the same temperature. This result is somewhat surprising as the surface stiffness of the particles in the HS phase is expected to be significantly lower, which should be reflected by the phase images [20]. However, the cross-talk between the topography changes and the phase signal may hide the effect related to the variation of the sample visocoelastic properties [26].…”

Section: Resultsmentioning

confidence: 99%

“…Up to now, mainly optical microscopy has been used for this aim in the SCO field (for examples see References [18,19] and references therein), but the limited spatial resolution of far-field optics makes this technique more suitable for the study of large single crystals several tenths of micrometers in size. In situ scanning probe microscopy [20,21,22,23,24] and electron microscopy [25] techniques have been only very recently employed on SCO materials, opening up exciting perspectives for the high spatial resolution analysis and manipulation of SCO objects in a broad size range. Here we present a variable-temperature AFM topography study of a nanocrystalline film of 1 with the aim to give a more comprehensive picture of the microstructural changes associated with the SCO in this sample.…”

Section: Introductionmentioning

confidence: 99%

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In Situ AFM Imaging of Microstructural Changes Associated with The Spin Transition in [Fe(Htrz)2(Trz)](Bf4) Nanoparticles

et al. 2016

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Topographic images of [Fe(Htrz) 2 (trz)](BF 4 ) nanoparticles were acquired across the first-order spin transition using variable-temperature atomic force microscopy (AFM) in amplitude modulation mode. These studies revealed a complex morphology of the particles consisting of aggregates of small nanocrystals, which expand, separate and re-aggregate due to the mechanical stress during the spin-state switching events. Both reversible (prompt or slow recovery) and irreversible effects (fatigue) on the particle morphology were evidenced and correlated with the spin crossover properties.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

In Situ AFM Imaging of Microstructural Changes Associated with The Spin Transition in [Fe(Htrz)2(Trz)](Bf4) Nanoparticles

et al. 2016

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“…[15][16][17][18][19][20][21][22][23][24][25][26][27] Most reported complexes with hysteretic SCO are mononuclear or polymeric Fe II com-pounds, typically with neutral or cationic overall charge. Our group has focused in the search for anionic SCO complexes to increase their processing capabilities when incorporated into hybrid materials.…”

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confidence: 99%

Enhanced Activity and Acid pH Stability of Prussian Blue-type Oxygen Evolution Electrocatalysts Processed by Chemical Etching

et al. 2016

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The development of upscalable oxygen evolving electrocatalysts from earth-abundant metals able to operate in neutral or acidic environments and low overpotentials remains a fundamental challenge for the realization of artificial photosynthesis. In this study, we report a highly active phase of heterobimetallic cyanide-bridged electrocatalysts able to promote water oxidation under neutral, basic (pH < 13), and acidic conditions (pH > 1). Cobalt–iron Prussian blue-type thin films, formed by chemical etching of Co(OH)1.0(CO3)0.5·nH2O nanocrystals, yield a dramatic enhancement of the catalytic performance toward oxygen production, when compared with previous reports for analogous materials. Electrochemical, spectroscopic, and structural studies confirm the excellent performance, stability, and corrosion resistance, even when compared with state-of-the-art metal oxide catalysts under moderate overpotentials and in a remarkably large pH range, including acid media where most cost-effective water oxidation catalysts are not useful. The origin of the superior electrocatalytic activity toward water oxidation appears to be in the optimized interfacial matching between catalyst and electrode surface obtained through this fabrication method.

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“…In the case of thin SCO films, we have recently demonstrated that atomic force microscopy (AFM) force spectroscopy allows the spin transition to be probed with high spatial resolution . This approach is based on the ubiquitous decrease of the elastic modulus of SCO materials (by ≈10–50%) when going from the LS to the HS phase .…”

Section: Comparison Of Reported Elastic Moduli Ofmentioning

confidence: 99%

Direct Visualization of Local Spin Transition Behaviors in Thin Molecular Films by Bimodal AFM

Shalabaeva

Bas

Piedrahita‐Bello

et al. 2019

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Thin films of the molecular spin‐crossover complex [Fe(HB(1,2,4‐triazol‐1‐yl)3)2] undergo spin transition above room temperature, which can be exploited in sensors, actuators, and information processing devices. Variable temperature viscoelastic mapping of the films by atomic force microscopy reveals a pronounced decrease of the elastic modulus when going from the low spin (5.2 ± 0.4 GPa) to the high spin (3.6 ± 0.2 GPa) state, which is also accompanied by increasing energy dissipation. This technique allows imaging, with high spatial resolution, of the formation of high spin puddles around film defects, which is ascribed to local strain relaxation. On the other hand, no clustering process due to cooperative phenomena was observed. This experimental approach sets the stage for the investigation of spin transition at the nanoscale, including phase nucleation and evolution as well as local strain effects.

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AFM Imaging of Molecular Spin‐State Changes through Quantitative Thermomechanical Measurements

Abstract: Quantitative atomic force microscopy is used in conjunction with microwire heaters for high-resolution imaging of the Young's modulus changes across the spin-state transition. When going from the high spin to the low spin state, a significant stiffening is observed.

Cited by 28 publications

References 35 publications

In Situ AFM Imaging of Microstructural Changes Associated with The Spin Transition in [Fe(Htrz)2(Trz)](Bf4) Nanoparticles

In Situ AFM Imaging of Microstructural Changes Associated with The Spin Transition in [Fe(Htrz)2(Trz)](Bf4) Nanoparticles

Enhanced Activity and Acid pH Stability of Prussian Blue-type Oxygen Evolution Electrocatalysts Processed by Chemical Etching

Direct Visualization of Local Spin Transition Behaviors in Thin Molecular Films by Bimodal AFM

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