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Spin Crossover and Solvate Effects in 1D FeII Chain Compounds Containing Bis(dipyridylamine)‐Linked Triazine Ligands

Identifieur interne : 006327 ( Main/Exploration ); précédent : 006326; suivant : 006328

Spin Crossover and Solvate Effects in 1D FeII Chain Compounds Containing Bis(dipyridylamine)‐Linked Triazine Ligands

Auteurs : Tamsyn M. Ross ; Boujemaa Moubaraki ; David. R. Turner ; Gregory J. Halder [États-Unis] ; Guillaume Chastanet [France] ; Suzanne M. Neville [France] ; John D. Cashion [Australie] ; Jean-François Létard [France] ; Stuart R. Batten ; Keith S. Murray [États-Unis]

Source :

RBID : ISTEX:FA3F44F769F69A0BFF7DB5A87DE56693335AA0B1

Descripteurs français

English descriptors

Abstract

A series of 1D polymeric FeII spin crossover (SCO) compounds of type trans‐[FeII(NCX)2(L)]·Solvent has been synthesised {L = DPPyT = 1‐[4,6‐bis(dipyridin‐2‐ylamino)‐1,3,5‐triazin‐2‐yl]pyridin‐4(1H)‐one for 1–4; NCX = NCS– for 1 and 2, NCSe– for 3 and 4; Solvent = 2.5CH2Cl2 for 1, 2CHCl3·0.5CH3OH for 2 and 4, CH2Cl2 for 3; L = DPT (6‐phenoxy‐N2,N2,N4,N4‐tetra‐2‐pyridinyl‐1,3,5‐triazine‐2,4‐diamine) for 5; NCX = NCS– for 5; Solvent = 2CH3OH·H2O for 5; L = DQT {4‐[4,6‐bis(dipyridin‐2‐ylamino)‐1,3,5‐triazin‐2‐yloxy]phenol} for 6–8; NCX– = NCS– for 6; Solvent = 2CH2Cl2 for 6; NCX– = NCSe– for 7; Solvent = CH2Cl2·CH2ClCH2Cl for 7; NCX– = NCSe– for 8; Solvent = 1.5CH2Cl2·0.5CH3OH for 8}. Two mononuclear complexes, trans‐[FeII(NCS)2(DPT)2]·2CH3OH (9) and trans‐[FeII(NCSe)2(DPT)2]·2CH3OH (10), contained the L ligand in a terminal bidentate coordination mode. As well as variations made in the NCX– ligands, variations were also made in substituent groups on the s‐triazine “core” of L to investigate their intermolecular/supramolecular role in crystal packing and, thus, their influence on SCO properties. All the complexes crystallised as solvates, and the influence of the latter on the magnetism and spin transitions was explored. A wide range of physical methods was employed, as a function of temperature, viz. crystallography, PXRD (synchrotron), susceptibilities, LIESST and Mössbauer effect, in order to probe magnetostructural correlations in these 1D families. New examples of half‐crossovers, with ordered –LS–HS–LS–HS– intrachain states existing below T1/2, have been observed and comparisons made to related one‐ or two‐step systems. All the observed transitions are gradual and non‐hysteretic, and brief comments are made in relation to recent theoretical models for cooperativity, developed elsewhere.

Url:
DOI: 10.1002/ejic.201000876


Affiliations:


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Le document en format XML

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<term>Asymmetric units</term>
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<term>Desolvated sample</term>
<term>Dichloromethane</term>
<term>Dichloromethane molecules</term>
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<term>Quadrupole splitting</term>
<term>Reaction vial</term>
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<term>Room temperature</term>
<term>Single crystal</term>
<term>Solvate</term>
<term>Solvated</term>
<term>Solvent</term>
<term>Solvent molecules</term>
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<term>Structural details</term>
<term>Susceptibility</term>
<term>Synchrotron</term>
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<term>Verlag</term>
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<term>Asymmetric units</term>
<term>Australian synchrotron</term>
<term>Beamline</term>
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<term>Biphasic mixture</term>
<term>Black spheres</term>
<term>Bond lengths</term>
<term>Calcd</term>
<term>Centre</term>
<term>Centroid</term>
<term>Chem</term>
<term>Closest interchain distance</term>
<term>Closest intrachain distance</term>
<term>Compounds cddt</term>
<term>Contact distances</term>
<term>Cooperativity</term>
<term>Crossover</term>
<term>Crystal lattice</term>
<term>Crystal structures</term>
<term>Crystal system space group</term>
<term>Crystallographic data</term>
<term>Data restraints parameters</term>
<term>Desolvated</term>
<term>Desolvated phase</term>
<term>Desolvated sample</term>
<term>Dichloromethane</term>
<term>Dichloromethane molecules</term>
<term>Different values</term>
<term>Diffraction data</term>
<term>Diffraction studies</term>
<term>Dimethyl sulfoxide</term>
<term>Doublet</term>
<term>Dppyt</term>
<term>Dppyt solution</term>
<term>Empirical formula formula mass</term>
<term>Experimental section</term>
<term>Feii</term>
<term>Feii centre</term>
<term>Feii centres</term>
<term>Feii chain compounds</term>
<term>Full desolvation</term>
<term>Full paper</term>
<term>Gamez</term>
<term>Gmbh</term>
<term>Gradual nature</term>
<term>Green light</term>
<term>High vacuum</term>
<term>Higher value</term>
<term>Hydrogen atoms</term>
<term>Hysteresis</term>
<term>Inorg</term>
<term>Interatomic parameters</term>
<term>Intermolecular</term>
<term>Intermolecular interactions</term>
<term>Isomer</term>
<term>Isomer shift</term>
<term>Kepert</term>
<term>Kgaa</term>
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<term>Lattice</term>
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<term>Magnetic character</term>
<term>Magnetic data</term>
<term>Magnetic susceptibility</term>
<term>Magnetic susceptibility measurements</term>
<term>Metal centres</term>
<term>Methanol</term>
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<term>Monash university</term>
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<term>Ncs2</term>
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<term>Orange crystals</term>
<term>Parent solvate</term>
<term>Photomagnetic</term>
<term>Quadrupole splitting</term>
<term>Reaction vial</term>
<term>Relaxation kinetics</term>
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<term>Single crystal</term>
<term>Solvate</term>
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<term>Structural details</term>
<term>Susceptibility</term>
<term>Synchrotron</term>
<term>Temperature decreases</term>
<term>Temperature range</term>
<term>Triazine</term>
<term>Triazine ring</term>
<term>Triclinic</term>
<term>Trigonal twist</term>
<term>Trigonal twist angle</term>
<term>Unique feii centres</term>
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<front>
<div type="abstract">A series of 1D polymeric FeII spin crossover (SCO) compounds of type trans‐[FeII(NCX)2(L)]·Solvent has been synthesised {L = DPPyT = 1‐[4,6‐bis(dipyridin‐2‐ylamino)‐1,3,5‐triazin‐2‐yl]pyridin‐4(1H)‐one for 1–4; NCX = NCS– for 1 and 2, NCSe– for 3 and 4; Solvent = 2.5CH2Cl2 for 1, 2CHCl3·0.5CH3OH for 2 and 4, CH2Cl2 for 3; L = DPT (6‐phenoxy‐N2,N2,N4,N4‐tetra‐2‐pyridinyl‐1,3,5‐triazine‐2,4‐diamine) for 5; NCX = NCS– for 5; Solvent = 2CH3OH·H2O for 5; L = DQT {4‐[4,6‐bis(dipyridin‐2‐ylamino)‐1,3,5‐triazin‐2‐yloxy]phenol} for 6–8; NCX– = NCS– for 6; Solvent = 2CH2Cl2 for 6; NCX– = NCSe– for 7; Solvent = CH2Cl2·CH2ClCH2Cl for 7; NCX– = NCSe– for 8; Solvent = 1.5CH2Cl2·0.5CH3OH for 8}. Two mononuclear complexes, trans‐[FeII(NCS)2(DPT)2]·2CH3OH (9) and trans‐[FeII(NCSe)2(DPT)2]·2CH3OH (10), contained the L ligand in a terminal bidentate coordination mode. As well as variations made in the NCX– ligands, variations were also made in substituent groups on the s‐triazine “core” of L to investigate their intermolecular/supramolecular role in crystal packing and, thus, their influence on SCO properties. All the complexes crystallised as solvates, and the influence of the latter on the magnetism and spin transitions was explored. A wide range of physical methods was employed, as a function of temperature, viz. crystallography, PXRD (synchrotron), susceptibilities, LIESST and Mössbauer effect, in order to probe magnetostructural correlations in these 1D families. New examples of half‐crossovers, with ordered –LS–HS–LS–HS– intrachain states existing below T1/2, have been observed and comparisons made to related one‐ or two‐step systems. All the observed transitions are gradual and non‐hysteretic, and brief comments are made in relation to recent theoretical models for cooperativity, developed elsewhere.</div>
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<name sortKey="Letard, Jean Rancois" sort="Letard, Jean Rancois" uniqKey="Letard J" first="Jean-François" last="Létard">Jean-François Létard</name>
<name sortKey="Neville, Suzanne M" sort="Neville, Suzanne M" uniqKey="Neville S" first="Suzanne M." last="Neville">Suzanne M. Neville</name>
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<name sortKey="Cashion, John D" sort="Cashion, John D" uniqKey="Cashion J" first="John D." last="Cashion">John D. Cashion</name>
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