Solvatomorphism, polymorphism and spin crossover in bis[hydrotris(1,2,3-triazol-1-yl)borate]iron(<scp>ii</scp>)

Horniichuk, Oleksandr Ye.; Ridier, Karl; Molnár, Gábor; Kotsyubynsky, Volodymyr; Shova, Sergiu; Amirkhanov, Vladimir M.; Gural'skiy, Il’ya A.; Salmon, Lionel; Bousseksou, Azzedine

doi:10.1039/d2nj01471h

Cited by 5 publications

(11 citation statements)

References 57 publications

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“…We use the thermal evolution of the highest intensity absorption band at 336 nm to follow the occurrence of a spin-state change in the films. Typical transition curves, displayed in Figure b, reveal a very gradual spin conversion between the LS and HS states, similar to the one observed in the bulk powder . The transition temperature is centered around 374 ± 2 K, independently of the film thickness (Figure c).…”

Section: Results and Discussionsupporting

confidence: 89%

“…320−430 K). 32 Here, we show that the complex 1 is sublimable and can be deposited in the form of high-quality, homogeneous thin films by vacuum thermal evaporation, in which the SCO properties are retained. The structural, morphological, and electronic properties of the films were investigated using grazing-incidence X-ray diffraction (GIXRD), atomic force microscopy (AFM), and variable-temperature ultraviolet− visible (UV−vis) spectrophotometry.…”

Section: Introductionmentioning

confidence: 75%

“…Typical transition curves, displayed in Figure 4b, reveal a very gradual spin conversion between the LS and HS states, similar to the one observed in the bulk powder. 32 The transition temperature is centered around 374 ± 2 K, independently of the film thickness (Figure 4c). The transition is virtually complete at 273 K (pure LS state), whereas a residual LS fraction of ca.…”

Section: Fabrication and Characterization Of [Fe(hb(123-triazol-1-yl)...mentioning

confidence: 93%

“…In this work, we demonstrate that the molecular SCO complex [Fe(HB(1,2,3-triazol-1-yl) 3 ) 2 ], 1 (see molecular and crystal structures, Figure S1), fulfills the above-mentioned conditions and can then be used as an accurate, continuous surface temperature sensor, probed by optical reflectivity. Indeed, contrary to its structural isomer [Fe(HB(1,2,4-triazol-1-yl) 3 ) 2 ], which was used in a previous work as a binary temperature sensor, the polycrystalline bulk powder of 1 presents a stable, gradual spin transition centered at around 373 K, spanning over a wide temperature range (ca.…”

Section: Introductionmentioning

confidence: 99%

“…Indeed, contrary to its structural isomer [Fe(HB(1,2,4-triazol-1-yl) 3 ) 2 ], which was used in a previous work as a binary temperature sensor, the polycrystalline bulk powder of 1 presents a stable, gradual spin transition centered at around 373 K, spanning over a wide temperature range (ca. 320–430 K) . Here, we show that the complex 1 is sublimable and can be deposited in the form of high-quality, homogeneous thin films by vacuum thermal evaporation, in which the SCO properties are retained.…”

Section: Introductionmentioning

confidence: 99%

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High-Sensitivity Microthermometry Method Based on Vacuum-Deposited Thin Films Exhibiting Gradual Spin Crossover above Room Temperature

Horniichuk

Ridier

Zhang

et al. 2022

ACS Appl. Mater. Interfaces

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We report on the fabrication, characterization, and microthermometry application of high-quality, nanometric thin films, with thicknesses in the range 20–200 nm, of the molecular spin-crossover complex [Fe(HB(1,2,3-triazol-1-yl)3)2]. The films were obtained by vacuum thermal evaporation and characterized by X-ray diffraction, UV spectrophotometry, and atomic force microscopy. The as-deposited films are dense and crystalline with a preferred [011] orientation of the monoclinic crystal lattice normal to the substrate surface. The films exhibit a gradual spin conversion centered at ca. 374 K spanning the 273–473 K temperature range, irrespective of their thickness. When deposited on a microelectronic device, these films can be used to enhance the UV-light thermoreflectance coefficient of reflective surfaces by more than an order of magnitude, allowing for high-sensitivity thermoreflectance thermal imaging.

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Section: Results and Discussionsupporting

confidence: 89%

Section: Introductionmentioning

confidence: 75%

Section: Fabrication and Characterization Of [Fe(hb(123-triazol-1-yl)...mentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

High-Sensitivity Microthermometry Method Based on Vacuum-Deposited Thin Films Exhibiting Gradual Spin Crossover above Room Temperature

Horniichuk

Ridier

Zhang

et al. 2022

ACS Appl. Mater. Interfaces

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Molecular and Electronic Structures, Spectra, Electrochemistry and Anti‐bacterial Efficacy of Novel Heterocyclic Hydrazones of Phenanthrenequinone and Their Nickel(II) Complexes

et al. 2022

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A pair of tridentate ligands incorporating heterocyclic hydrazones of 9,10‐phenanthrenequinone viz,. pyridyl‐hydrazino‐phenathrenequinone HLPy 1a and benzothiazolyl‐hydrazino‐phenathrenequinone HLBenz 1b have been synthesized and both behave as monoanionic towards nickel(II), forming meridional octahedral complexes of type [Ni(LPy)2] 2a and [Ni(LBenz)2] 2b as evident from single crystal X‐ray diffraction studies. The complexes are electro‐active in solution and nature of redox orbitals has been analysed by theoretical means. They display two oxidative and two reductive responses that have been ascribed to the redox processes of coordinated ligands. The electronic absorption spectral patterns of two complexes are analogous barring the fact that lower energy transition for 2b is marginally bathochromically shifted relative to that of 2a and it has been clarified by TD‐DFT studies. Anti‐bacterial efficacy of the ligands HLPy 1a, HLBenz 1b and complexes [Ni(LPy)2] 2a, [Ni(LBenz)2] 2b against four Gram‐positive and four Gram‐negative strains has been explored. [Ni(LPy)2] 2a exhibits more pronounced efficacy than [Ni(LBenz)2] 2b and these are greater than those of the corresponding ligands. The mode of action of 2a is essential via DNA damage while protein leakage and membrane lipid damage were observed upon treatment with 2b.

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Reversible Switching of Strong Light–Matter Coupling Using Spin-Crossover Molecular Materials

Zhang

Ridier

Horniichuk

et al. 2023

J. Phys. Chem. Lett.

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The formation of hybrid light−matter states through the resonant interaction of confined electromagnetic fields with matter excitations has emerged as a fascinating tool for controlling quantum-mechanical states and then manipulating the functionalities and chemical reactivity landscape of molecular materials. Here we report the first observation of switchable strong light−matter coupling involving bistable spin-crossover molecules. Spectroscopic measurements, supported by transfer-matrix and coupled-oscillator simulations, reveal Rabi splitting values of up to 550 meV, which at 15% of the molecular excitation energy enter the regime of ultrastrong coupling. We find that the thermally induced switching of molecules between their low-spin and high-spin states allows fine control of the light−matter hybridization strength, offering the appealing possibility of reversible switching between the ultrastrong-and weak-coupling regimes within a single photonic structure. Through this work, we show that spin-crossover molecular compounds constitute a promising class of active nanomaterials in the burgeoning context of tunable polaritonic devices and polaritonic chemistry.

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Solvatomorphism, polymorphism and spin crossover in bis[hydrotris(1,2,3-triazol-1-yl)borate]iron(ii)

Abstract: Solvatomorphism and polymorphism play a crutial role in defining charachteristics of spin crossover (SCO) in coordination compounds. In this paper we describe a detailed characterization of the SCO bis[hydrotris(1,2,3-triazol-1-yl)borate]iron(II) complex...

Cited by 5 publications

References 57 publications

High-Sensitivity Microthermometry Method Based on Vacuum-Deposited Thin Films Exhibiting Gradual Spin Crossover above Room Temperature

High-Sensitivity Microthermometry Method Based on Vacuum-Deposited Thin Films Exhibiting Gradual Spin Crossover above Room Temperature

Molecular and Electronic Structures, Spectra, Electrochemistry and Anti‐bacterial Efficacy of Novel Heterocyclic Hydrazones of Phenanthrenequinone and Their Nickel(II) Complexes

Reversible Switching of Strong Light–Matter Coupling Using Spin-Crossover Molecular Materials

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