Formation of Metallic Polyferrocene Chains under Pressure

Gain, Pranab; Jana, Rajkumar; Datta, Ayan

doi:10.1021/acs.jpca.1c01205

Cited by 12 publications

(8 citation statements)

References 50 publications

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“…The low-pressure (<2 GPa, C 2v ) and high-pressure (>2 GPa, D 4h ) phases of Fe(CO) 4 were fitted to a third-order Birch–Murnaghan P – V relationship to obtain the bulk modulus ( K 0 ) and pressure derivative of the bulk modulus ( K 0 ′ ) . For the C 2v phase, K 0 and K 0 ′ are 30.0 GPa and 4.3, respectively, while for the D 4h phase, K 0 and K 0 ′ are 38.0 GPa and 4.9, respectively (see the Supporting Information File, Figure S1 for fitting details).…”

Section: Resultsmentioning

confidence: 99%

Compression Produces a Square-Planar Iron Tetracarbonyl

2022

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Iron carbonyls are known to form 18-electron complexes like Fe(CO)5, Fe2(CO)9, and Fe3(CO)12 having terminal or bridged Fe–CO bonding. Based on genetic algorithm-assisted density functional theory (DFT) calculations, it is predicted that at pressures above 2 GPa, iron tetracarbonyl, Fe(CO)4, attains a square-planar geometry with a 16-electron count. Compression overcomes the [Ar]4s23d6 (S = 2) → [Ar]4s03d8 (S = 0) excitation energy to stabilize a closed-shell Fe(CO)4 with a d8-configuration. Strong σ(4CO) → Fe (d x 2 –y 2) bonding along with Fe(d xz , d yz ) and Fe(d xy ) → π (CO)4* back-bonding assists the formation of square-planar Fe(CO)4 under pressure. Compression progressively flattens and destabilizes the ambient pressure C2v structure of Fe(CO)4, and beyond 2 GPa, it undergoes a sharp C2v → D4h transition with ΔV unit‑cell = 2.1% and trans-θ(OC–Fe–CO) = 180°. Realizing a square-planar geometry in a four-coordinated Fe-carbonyl complex shows the rich prospects of the new chemistry under pressure.

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Section: Resultsmentioning

confidence: 99%

Compression Produces a Square-Planar Iron Tetracarbonyl

2022

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“…α was approximated as a finite difference quotient and hence the Raman intensity of the mode was found. All these calculations were performed using a python script [37] interfaced with VASP simulation code [33].…”

Section: Computational Detailsmentioning

confidence: 99%

Spin-crossover assisted metallization of few-layer FePS$_3$ at 1.45 GPa

Mallick¹,

Palit²,

Jana³

et al. 2023

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Magnetic insulators in reduced dimension are the ideal model systems to study spincrossover (SCO) induced cooperative behavior under pressure. Similar to the external perturbations like light illumination or temperature, external pressure may provide new pathway to accelerate giant lattice collapse, and subsequently Mott transition in van der Waals (vdW) materials with diminishing effect of the third dimension. Here, we investigate room-temperature layer-dependent SCO and insulator-metal transition (IMT) in vdW magnet, FePS 3 , under high pressure using micro-Raman scattering.Experimentally obtained spectra, in agreement with the computed Raman modes, indicates evidence of IMT of FePS 3 started off with a spin-state transition from a high (S = 2) to low spin state (S = 0) with a thickness dependent critical pressure (P c ) which reduces to 1.45 GPa in 3-layer flakes compared to 10.8 GPa for the bulk counterpart.Additionally, a broad Raman mode (P * ) emerges between 310 cm −1 and 370 cm −1 at elevated pressure for three different thicknesses of FePS 3 flakes (3 -100 layers), also corroborated with computational results which suggests the pressure dependent decrease of metal-ligand bond distance (Fe-S) with lowering of magnetic moment in FePS 3 . Phenomenologically, our results in few-layer flakes with strong structural anisotropy which enhances the in-plane strain with applied pressure can be understood by adopting Hubbard model and considering the spectral-range (bandwidth W ) as a function of layer numbers (L) and pressure (P ) with a power-law scaling.Reduction of the critical pressure for phase transition in few-layer vdW magnets to 1-2 GPa marks the possibility of using nano-enclosure fit for use in device electronics where the pressure is induced due to interfacial adhesion, like in vdW heterostructure or molecules trapped between layers, and thereby, avoiding the conventional use of diamond anvil cell (DAC).

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“…Since the milestone discovery of ferrocene, 1 the multidecker molecular complexes in the form of sandwich clusters and their infinitely extended nanowires have attracted great research interest due to the distinct structural, optical, 2,3 chemical, 4 electrical, 5 and magnetic properties, 6 rendering them potential candidates in catalysis, 7 electronics and spintronics. 8–12 Especially, the tunable coordination mode between the central metal and organic molecules accompanied by diverse charge transfer and crystal field splitting can lead to unpaired d electrons and form intriguing magnetic ordering phenomena. 13–15 For instance, the organometallic complexes composed of vanadium and benzene, V n (Bz) m (Bz = C 6 H 6 ), were confirmed to be molecular magnets and the magnetic moments of the complexes increase with the central metal atoms.…”

Section: Introductionmentioning

confidence: 99%