Halogen Substitution Effects on N2 O Schiff Base Ligands in Unprecedented Abrupt Fe(II) Spin Crossover Complexes.
Identifieur interne : 000B11 ( Main/Exploration ); précédent : 000B10; suivant : 000B12Halogen Substitution Effects on N2 O Schiff Base Ligands in Unprecedented Abrupt Fe(II) Spin Crossover Complexes.
Auteurs : Wasinee Phonsri [Australie] ; David S. Macedo [Australie] ; Kuduva R. Vignesh [Inde] ; Gopalan Rajaraman [Inde] ; Casey G. Davies [Nouvelle-Zélande] ; Guy N L. Jameson [Nouvelle-Zélande] ; Boujemaa Moubaraki [Australie] ; Jas S. Ward [Nouvelle-Zélande] ; Paul E. Kruger [Nouvelle-Zélande] ; Guillaume Chastanet [France] ; Keith S. Murray [Australie]Source :
- Chemistry (Weinheim an der Bergstrasse, Germany) [ 1521-3765 ] ; 2017.
Abstract
A family of halogen-substituted Schiff base iron(II) complexes, [Fe(II) (qsal-X)2 ], (qsal-X=5-X-N-(8-quinolyl)salicylaldimines)) in which X=F (1), Cl (2), Br (3) or I (4) has been investigated in detail. Compound 1 shows a temperature invariant high spin state, whereas the others all show abrupt spin transitions, at or above room temperature, namely, 295 K (X=I) up to 342 K (X=Br), these being some of the highest T1/2 values obtained, to date, for Fe(II) N/O species. We have recently reported subtle symmetry breaking in [Fe(II) (qsal-Cl)2 ] 2 with two spin transition steps occurring at 308 and 316 K. A photomagnetic study reveals almost full HS conversion of [Fe(II) (qsal-I)2 ] 4 at low temperature (T(LIESST)=54 °K). The halogen substitution effects on the magnetic properties, as well as the crystal packing of the [Fe(II) (qsal-X)2 ] compounds and theoretical calculations, are discussed in depth, giving important knowledge for the design of new spin crossover materials. In comparison to the well known iron(III) analogues, [Fe(III) (qsal-X)2 ](+) , the two extra π-π and P4AE interactions found in [Fe(II) (qsal-X)2 ] compounds, are believed to be accountable for the spin transitions occurring at ambient temperatures.
DOI: 10.1002/chem.201700232
PubMed: 28474778
Affiliations:
- Australie, France, Inde, Nouvelle-Zélande
- Aquitaine, Nouvelle-Aquitaine
- Bordeaux
- Université de Bordeaux
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Vignesh</name><affiliation wicri:level="1"><nlm:affiliation>IITB-Monash Research Academy, IIT Bombay, Mumbai, 400076, India.</nlm:affiliation><country xml:lang="fr">Inde</country><wicri:regionArea>IITB-Monash Research Academy, IIT Bombay, Mumbai, 400076</wicri:regionArea><wicri:noRegion>400076</wicri:noRegion></affiliation></author><author><name sortKey="Rajaraman, Gopalan" sort="Rajaraman, Gopalan" uniqKey="Rajaraman G" first="Gopalan" last="Rajaraman">Gopalan Rajaraman</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, Indian Institute of Technology, Mumbai, 400076, India.</nlm:affiliation><country xml:lang="fr">Inde</country><wicri:regionArea>Department of Chemistry, Indian Institute of Technology, Mumbai, 400076</wicri:regionArea><wicri:noRegion>400076</wicri:noRegion></affiliation></author><author><name sortKey="Davies, Casey G" sort="Davies, Casey G" uniqKey="Davies C" first="Casey G" last="Davies">Casey G. Davies</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Otago, Dunedin, 9054, New Zealand.</nlm:affiliation><country xml:lang="fr">Nouvelle-Zélande</country><wicri:regionArea>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Otago, Dunedin, 9054</wicri:regionArea><wicri:noRegion>9054</wicri:noRegion></affiliation></author><author><name sortKey="Jameson, Guy N L" sort="Jameson, Guy N L" uniqKey="Jameson G" first="Guy N L" last="Jameson">Guy N L. Jameson</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Otago, Dunedin, 9054, New Zealand.</nlm:affiliation><country xml:lang="fr">Nouvelle-Zélande</country><wicri:regionArea>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Otago, Dunedin, 9054</wicri:regionArea><wicri:noRegion>9054</wicri:noRegion></affiliation></author><author><name sortKey="Moubaraki, Boujemaa" sort="Moubaraki, Boujemaa" uniqKey="Moubaraki B" first="Boujemaa" last="Moubaraki">Boujemaa Moubaraki</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800</wicri:regionArea><wicri:noRegion>3800</wicri:noRegion></affiliation></author><author><name sortKey="Ward, Jas S" sort="Ward, Jas S" uniqKey="Ward J" first="Jas S" last="Ward">Jas S. Ward</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Canterbury, Private Bag 4800, Christchurch, 8041, New Zealand.</nlm:affiliation><country xml:lang="fr">Nouvelle-Zélande</country><wicri:regionArea>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Canterbury, Private Bag 4800, Christchurch, 8041</wicri:regionArea><wicri:noRegion>8041</wicri:noRegion></affiliation></author><author><name sortKey="Kruger, Paul E" sort="Kruger, Paul E" uniqKey="Kruger P" first="Paul E" last="Kruger">Paul E. Kruger</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Canterbury, Private Bag 4800, Christchurch, 8041, New Zealand.</nlm:affiliation><country xml:lang="fr">Nouvelle-Zélande</country><wicri:regionArea>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Canterbury, Private Bag 4800, Christchurch, 8041</wicri:regionArea><wicri:noRegion>8041</wicri:noRegion></affiliation></author><author><name sortKey="Chastanet, Guillaume" sort="Chastanet, Guillaume" uniqKey="Chastanet G" first="Guillaume" last="Chastanet">Guillaume Chastanet</name><affiliation wicri:level="4"><nlm:affiliation>CNRS, Université de Bordeaux, ICMCB, 87 avenue du Dr. A. Schweitzer, Pessac, 33608, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>CNRS, Université de Bordeaux, ICMCB, 87 avenue du Dr. A. Schweitzer, Pessac, 33608</wicri:regionArea><wicri:noRegion>33608</wicri:noRegion><orgName type="university">Université de Bordeaux</orgName><placeName><settlement type="city">Bordeaux</settlement><region type="region" nuts="2">Nouvelle-Aquitaine</region><region type="old region" nuts="2">Aquitaine</region></placeName></affiliation></author><author><name sortKey="Murray, Keith S" sort="Murray, Keith S" uniqKey="Murray K" first="Keith S" last="Murray">Keith S. Murray</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800</wicri:regionArea><wicri:noRegion>3800</wicri:noRegion></affiliation></author></analytic><series><title level="j">Chemistry (Weinheim an der Bergstrasse, Germany)</title><idno type="eISSN">1521-3765</idno><imprint><date when="2017" type="published">2017</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">A family of halogen-substituted Schiff base iron(II) complexes, [Fe(II) (qsal-X)2 ], (qsal-X=5-X-N-(8-quinolyl)salicylaldimines)) in which X=F (1), Cl (2), Br (3) or I (4) has been investigated in detail. Compound 1 shows a temperature invariant high spin state, whereas the others all show abrupt spin transitions, at or above room temperature, namely, 295 K (X=I) up to 342 K (X=Br), these being some of the highest T1/2 values obtained, to date, for Fe(II) N/O species. We have recently reported subtle symmetry breaking in [Fe(II) (qsal-Cl)2 ] 2 with two spin transition steps occurring at 308 and 316 K. A photomagnetic study reveals almost full HS conversion of [Fe(II) (qsal-I)2 ] 4 at low temperature (T(LIESST)=54 °K). The halogen substitution effects on the magnetic properties, as well as the crystal packing of the [Fe(II) (qsal-X)2 ] compounds and theoretical calculations, are discussed in depth, giving important knowledge for the design of new spin crossover materials. In comparison to the well known iron(III) analogues, [Fe(III) (qsal-X)2 ](+) , the two extra π-π and P4AE interactions found in [Fe(II) (qsal-X)2 ] compounds, are believed to be accountable for the spin transitions occurring at ambient temperatures.</div></front></TEI><affiliations><list><country><li>Australie</li><li>France</li><li>Inde</li><li>Nouvelle-Zélande</li></country><region><li>Aquitaine</li><li>Nouvelle-Aquitaine</li></region><settlement><li>Bordeaux</li></settlement><orgName><li>Université de Bordeaux</li></orgName></list><tree><country name="Australie"><noRegion><name sortKey="Phonsri, Wasinee" sort="Phonsri, Wasinee" uniqKey="Phonsri W" first="Wasinee" last="Phonsri">Wasinee Phonsri</name></noRegion><name sortKey="Macedo, David S" sort="Macedo, David S" uniqKey="Macedo D" first="David S" last="Macedo">David S. Macedo</name><name sortKey="Moubaraki, Boujemaa" sort="Moubaraki, Boujemaa" uniqKey="Moubaraki B" first="Boujemaa" last="Moubaraki">Boujemaa Moubaraki</name><name sortKey="Murray, Keith S" sort="Murray, Keith S" uniqKey="Murray K" first="Keith S" last="Murray">Keith S. Murray</name></country><country name="Inde"><noRegion><name sortKey="Vignesh, Kuduva R" sort="Vignesh, Kuduva R" uniqKey="Vignesh K" first="Kuduva R" last="Vignesh">Kuduva R. Vignesh</name></noRegion><name sortKey="Rajaraman, Gopalan" sort="Rajaraman, Gopalan" uniqKey="Rajaraman G" first="Gopalan" last="Rajaraman">Gopalan Rajaraman</name></country><country name="Nouvelle-Zélande"><noRegion><name sortKey="Davies, Casey G" sort="Davies, Casey G" uniqKey="Davies C" first="Casey G" last="Davies">Casey G. Davies</name></noRegion><name sortKey="Jameson, Guy N L" sort="Jameson, Guy N L" uniqKey="Jameson G" first="Guy N L" last="Jameson">Guy N L. Jameson</name><name sortKey="Kruger, Paul E" sort="Kruger, Paul E" uniqKey="Kruger P" first="Paul E" last="Kruger">Paul E. Kruger</name><name sortKey="Ward, Jas S" sort="Ward, Jas S" uniqKey="Ward J" first="Jas S" last="Ward">Jas S. Ward</name></country><country name="France"><region name="Nouvelle-Aquitaine"><name sortKey="Chastanet, Guillaume" sort="Chastanet, Guillaume" uniqKey="Chastanet G" first="Guillaume" last="Chastanet">Guillaume Chastanet</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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