Dataset Information

Bistable Hofmann-Type Fe^II Spin-Crossover Two-Dimensional Polymers of 4-Alkyldisulfanylpyridine for Prospective Grafting of Monolayers on Metallic Surfaces.

ABSTRACT: Aiming at investigating the suitability of Hofmann-type two-dimensional (2D) coordination polymers {Fe^II(L_ax)₂[M^II(CN)₄]} to be processed as single monolayers and probed as spin crossover (SCO) junctions in spintronic devices, the synthesis and characterization of the M^II derivatives (M^II = Pd and Pt) with sulfur-rich axial ligands (L_ax = 4-methyl- and 4-ethyl-disulfanylpyridine) have been conducted. The thermal dependence of the magnetic and calorimetric properties confirmed the occurrence of strong cooperative SCO behavior in the temperature interval of 100-225 K, featuring hysteresis loops 44 and 32.5 K/21 K wide for Pt^II-methyl and Pt^II/Pd^II-ethyl derivatives, while the Pd^II-methyl derivative undergoes a much less cooperative multistep SCO. Excluding Pt^II-methyl, the remaining compounds display light-induced excited spin-state trapping at 10 K with T_LIESST temperatures in the range of 50-70 K. Single-crystal studies performed in the temperature interval 100-250 K confirmed the layered structure and the occurrence of complete transformation between the high- and low-spin states of the Fe^II center for the four compounds. Strong positional disorder seems to be the source of elastic frustration driving the multistep SCO observed for the Pd^II-methyl derivative. It is expected that the peripheral disulfanyl groups will favor anchoring and growing of the monolayer on gold substrates and optimal electron transport in the device.

SUBMITTER: Turo-Cortes R

PROVIDER: S-EPMC9129067 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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Bistable Hofmann-Type FeII Spin-Crossover Two-Dimensional Polymers of 4-Alkyldisulfanylpyridine for Prospective Grafting of Monolayers on Metallic Surfaces.

Turo-Cortés Rubén R Valverde-Muñoz Francisco Javier FJ Meneses-Sánchez Manuel M Muñoz M Carmen MC Bartual-Murgui Carlos C Real José Antonio JA

Inorganic chemistry 20210528 12

Aiming at investigating the suitability of Hofmann-type two-dimensional (2D) coordination polymers {FeII(Lax)2[MII(CN)4]} to be processed as single monolayers and probed as spin crossover (SCO) junctions in spintronic devices, the synthesis and characterization of the MII derivatives (MII = Pd and Pt) with sulfur-rich axial ligands (Lax = 4-methyl- and 4-ethyl-disulfanylpyridine) have been conducted. The ther ...[more]

PMID: 34047556

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Project description:A multistable spin crossover (SCO) molecular alloy system [Fe1-x M x (nBu-im)3(tren)](P1-y As y F6)2 (M = ZnII, NiII; (nBu-im)3(tren) = tris(n-butyl-imidazol(2-ethylamino))amine) has been synthesized and characterized. By controlling the composition of this isomorphous series, two cooperative thermally induced SCO events featuring distinct critical temperatures (T c) and hysteresis widths (ΔT c, memory) can be selected at will. The pristine derivative 100As (x = 0, y = 1) displays a strong cooperative two-step SCO and two reversible structural phase transitions (PTs). The low temperature PTLT and the SCO occur synchronously involving conformational changes of the ligand's n-butyl arms and two different arrangements of the AsF6 - anions [T1c = 174 K (ΔT1c = 17 K), T2c = 191 K (ΔT2c = 23 K) (scan rate 2 K min-1)]. The high-temperature PTHT takes place in the high-spin state domain and essentially involves rearrangement of the AsF6 - anions [TPTc = 275 K (ΔTPTc = 16 K)]. This behavior strongly contrasts with that of the homologous 100P [x = 0, y = 0] derivative where two separate cooperative one-step SCO can be selected by controlling the kinetics of the coupled PTLT at ambient pressure: (i) one at low temperatures, T c = 122 K (ΔT c = 9 K), for temperature scan rates (>1 K min-1) (memory channel A) where the structural modifications associated with PTLS are inhibited; (ii) the other centered at T c = 155 K (ΔT c = 41 K) for slower temperature scan rates ≤0.1 K min-1 (memory channel B). These two SCO regimes of the 100P derivative transform reversibly into the two-step SCO of 100As upon application of hydrostatic pressure (ca. 0.1 GPa) denoting the subtle effect of internal chemical pressure on the SCO behavior. Precise control of AsF6 - ↔ PF6 - substitution, and hence of the PTLT kinetics, selectively selects the memory channel B of 100P when x = 0 and y ≈ 0.7. Meanwhile, substitution of FeII with ZnII or NiII [x ≈ 0.2, y = 0] favors the low temperature memory channel A at any scan rate. This intriguing interplay between PT, SCO and isomorphous substitution was monitored by single crystal and powder X-ray diffractometries, and magnetic and calorimetric measurements.

Dataset Information

Bistable Hofmann-Type Fe^II Spin-Crossover Two-Dimensional Polymers of 4-Alkyldisulfanylpyridine for Prospective Grafting of Monolayers on Metallic Surfaces.

Publications

Bistable Hofmann-Type Fe<sup>II</sup> Spin-Crossover Two-Dimensional Polymers of 4-Alkyldisulfanylpyridine for Prospective Grafting of Monolayers on Metallic Surfaces.

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