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Synergetic effect of host-guest chemistry and spin crossover in 3D hofmann-like metal-organic frameworks [Fe(bpac)M(CN) 4] (M=Pt, Pd, Ni)

Bartual-Murgui, C., Salmon, L., Akou, A., Ortega-Villar, N.A., Shepherd, H.J., Muñoz, M.C., Molnár, G., Real, J.A., Bousseksou, A. (2012) Synergetic effect of host-guest chemistry and spin crossover in 3D hofmann-like metal-organic frameworks [Fe(bpac)M(CN) 4] (M=Pt, Pd, Ni). Chemistry - A European Journal, 18 (2). pp. 507-516. ISSN 09476539 (ISSN). E-ISSN 1521-3765. (doi:10.1002/chem.201102357) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided) (KAR id:50831)

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The synthesis and characterization of a series of three-dimensional (3D) Hofmann-like clathrate porous metal-organic framework (MOF) materials [Fe(bpac)M(CN) 4] (M=Pt, Pd, and Ni; bpac=bis(4-pyridyl)acetylene) that exhibit spin-crossover behavior is reported. The rigid bpac ligand is longer than the previously used azopyridine and pyrazine and has been selected with the aim to improve both the spin-crossover properties and the porosity of the corresponding porous coordination polymers (PCPs). The 3D network is composed of successive {Fe[M(CN) 4]} n planar layers bridged by the bis-monodentate bpac ligand linked in the apical positions of the iron center. The large void between the layers, which represents 41.7% of the unit cell, can accommodate solvent molecules or free bpac ligand. Different synthetic strategies were used to obtain a range of spin-crossover behaviors with hysteresis loops around room temperature; the samples were characterized by magnetic susceptibility, calorimetric, Mössbauer, and Raman measurements. The complete physical study reveals a clear relationship between the quantity of included bpac molecules and the completeness of the spin transition, thereby underlining the key role of the Ï?-Ï? stacking interactions operating between the host and guest bpac molecules within the network. Although the inclusion of the bpac molecules tends to increase the amount of active iron centers, no variation of the transition temperature was measured. We have also investigated the ability of the network to accommodate the inclusion of molecules other than water and bpac and studied the synergy between the host-guest interaction and the spin-crossover behavior. In fact, the clathration of various aromatic molecules revealed specific modifications of the transition temperature. Finally, the transition temperature and the completeness of the transition are related to the nature of the metal associated with the iron center (Ni, Pt, or Pd) and also to the nature and the amount of guest molecules in the lattice. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Item Type: Article
DOI/Identification number: 10.1002/chem.201102357
Additional information: Unmapped bibliographic data: LA - English [Field not mapped to EPrints] J2 - Chem. Eur. J. [Field not mapped to EPrints] AD - Laboratoire de Chimie de Coordination, CNRS UPR-8241, INPT, 31077 Toulouse, France [Field not mapped to EPrints] AD - Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedratico Jose Beltran Martinez 2, 46980 Paterna (Valencia), Spain [Field not mapped to EPrints] AD - Departamento de Química Inorgánica, Universidad Autõnoma de México (UNAM), México D. F., 04510, Mexico [Field not mapped to EPrints] AD - Departamento de Física Aplicada, Universitat Politècnica de València, Camino de Vera s/n, 46022, Valencia, Spain [Field not mapped to EPrints] DB - Scopus [Field not mapped to EPrints]
Uncontrolled keywords: adsorption, host-guest systems, metal-organic frameworks, microporous materials, spin crossover, 3D networks, Apical positions, Aromatic molecules, Azopyridine, Clathration, Guest molecules, Host guest interactions, Host-guest system, Hostguest chemistry, Iron centers, Metal organic framework, Metal organic framework materials, Microporous, Mossbauer, Planar layers, Porous coordination polymer, Pyrazines, Raman measurements, Room temperature, Solvent molecules, Spin crossovers, Spin transition, Stacking interaction, Synergetic effect, Synthetic strategies, Three-dimensional (3D), Unit cells, Acetylene, Adsorption, Characterization, Hydrates, Iron, Ligands, Magnetic materials, Magnetic susceptibility, Metals, Microporous materials, Molecules, Molybdenum, Organic polymers, Platinum, Temperature, Three dimensional, Palladium
Subjects: Q Science > QD Chemistry > QD473 Physical properties in relation to structure
Divisions: Divisions > Division of Natural Sciences > Physics and Astronomy
Depositing User: Giles Tarver
Date Deposited: 22 Oct 2015 08:18 UTC
Last Modified: 16 Nov 2021 10:21 UTC
Resource URI: (The current URI for this page, for reference purposes)
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