Reversible guest-induced gate-opening with multiplex spin crossover responses in two-dimensional Hofmann clathrates.

Autor: Turo-Cortés R; Departamento de Química Inorgánica, Instituto de Ciencia Molecular (ICMol), Universidad de Valencia Valencia Spain carlos.bartual@uv.es jose.a.real@uv.es., Bartual-Murgui C; Departamento de Química Inorgánica, Instituto de Ciencia Molecular (ICMol), Universidad de Valencia Valencia Spain carlos.bartual@uv.es jose.a.real@uv.es., Castells-Gil J; Departamento de Química Inorgánica, Instituto de Ciencia Molecular (ICMol), Universidad de Valencia Valencia Spain carlos.bartual@uv.es jose.a.real@uv.es., Muñoz MC; Departamento de Física Aplicada, Universitat Politècnica de València Camino de Vera s/n E-46022 Valencia Spain., Martí-Gastaldo C; Departamento de Química Inorgánica, Instituto de Ciencia Molecular (ICMol), Universidad de Valencia Valencia Spain carlos.bartual@uv.es jose.a.real@uv.es., Real JA; Departamento de Química Inorgánica, Instituto de Ciencia Molecular (ICMol), Universidad de Valencia Valencia Spain carlos.bartual@uv.es jose.a.real@uv.es.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2020 Sep 22; Vol. 11 (41), pp. 11224-11234. Date of Electronic Publication: 2020 Sep 22.
DOI: 10.1039/d0sc04246c
Abstrakt: Spin crossover (SCO) compounds are very attractive types of switchable materials due to their potential applications in memory devices, actuators or chemical sensors. Rational chemical tailoring of these switchable compounds is key for achieving new functionalities in synergy with the spin state change. However, the lack of precise structural information required to understand the chemical principles that control the SCO response with external stimuli may eventually hinder further development of spin switching-based applications. In this work, the functionalization with an amine group in the two-dimensional (2D) SCO compound {Fe(5-NH 2 Pym) 2 [M II (CN) 4 ]} ( 1M , 5-NH 2 Pym = 5-aminopyrimidine, M II = Pt ( 1Pt ), Pd ( 1Pd )) confers versatile host-guest chemistry and structural flexibility to the framework primarily driven by the generation of extensive H-bond interactions. Solvent free 1M species reversibly adsorb small protic molecules such as water, methanol or ethanol yielding the 1M·H2O , 1M·0.5MeOH or 1M·xEtOH ( x = 0.25-0.40) solvated derivatives. Our results demonstrate that the reversible structural rearrangements accompanying these adsorption/desorption processes ( 1M ↔ 1M·guest ) follow a gate-opening mechanism whose kinetics depend not only on the nature of the guest molecule and that of the host framework ( 1Pt or 1Pd ) but also on their reciprocal interactions. In addition, a predictable and reversible guest-induced SCO modulation has been observed and accurately correlated with the associated crystallographic transformations monitored in detail by single crystal X-ray diffraction.
Competing Interests: There are no conflicts to declare.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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