Halogen Substitution Effects on N2 O Schiff Base Ligands in Unprecedented Abrupt Fe(II) Spin Crossover Complexes.
Identifieur interne : 000C09 ( PubMed/Curation ); précédent : 000C08; suivant : 000C10Halogen 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
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Macedo</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></affiliation></author><author><name sortKey="Vignesh, Kuduva R" sort="Vignesh, Kuduva R" uniqKey="Vignesh K" first="Kuduva R" last="Vignesh">Kuduva R. 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></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></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></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></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></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></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></affiliation></author><author><name sortKey="Chastanet, Guillaume" sort="Chastanet, Guillaume" uniqKey="Chastanet G" first="Guillaume" last="Chastanet">Guillaume Chastanet</name><affiliation wicri:level="1"><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></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></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><pubmed><MedlineCitation Status="In-Data-Review" Owner="NLM"><PMID Version="1">28474778</PMID><DateCreated><Year>2017</Year><Month>05</Month><Day>05</Day></DateCreated><DateRevised><Year>2017</Year><Month>05</Month><Day>26</Day></DateRevised><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1521-3765</ISSN><JournalIssue CitedMedium="Internet"><Volume>23</Volume><Issue>29</Issue><PubDate><Year>2017</Year><Month>May</Month><Day>23</Day></PubDate></JournalIssue><Title>Chemistry (Weinheim an der Bergstrasse, Germany)</Title><ISOAbbreviation>Chemistry</ISOAbbreviation></Journal><ArticleTitle>Halogen Substitution Effects on N2 O Schiff Base Ligands in Unprecedented Abrupt Fe(II) Spin Crossover Complexes.</ArticleTitle><Pagination><MedlinePgn>7052-7065</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1002/chem.201700232</ELocationID><Abstract><AbstractText>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.</AbstractText><CopyrightInformation>© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</CopyrightInformation></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Phonsri</LastName><ForeName>Wasinee</ForeName><Initials>W</Initials><Identifier Source="ORCID">http://orcid.org/0000-0001-7377-7484</Identifier><AffiliationInfo><Affiliation>School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Macedo</LastName><ForeName>David S</ForeName><Initials>DS</Initials><AffiliationInfo><Affiliation>School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Vignesh</LastName><ForeName>Kuduva R</ForeName><Initials>KR</Initials><AffiliationInfo><Affiliation>IITB-Monash Research Academy, IIT Bombay, Mumbai, 400076, India.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Rajaraman</LastName><ForeName>Gopalan</ForeName><Initials>G</Initials><Identifier Source="ORCID">http://orcid.org/0000-0001-6133-3026</Identifier><AffiliationInfo><Affiliation>Department of Chemistry, Indian Institute of Technology, Mumbai, 400076, India.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Davies</LastName><ForeName>Casey G</ForeName><Initials>CG</Initials><AffiliationInfo><Affiliation>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Otago, Dunedin, 9054, New Zealand.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Jameson</LastName><ForeName>Guy N L</ForeName><Initials>GNL</Initials><Identifier Source="ORCID">http://orcid.org/0000-0001-9416-699X</Identifier><AffiliationInfo><Affiliation>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Otago, Dunedin, 9054, New Zealand.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Moubaraki</LastName><ForeName>Boujemaa</ForeName><Initials>B</Initials><AffiliationInfo><Affiliation>School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Ward</LastName><ForeName>Jas S</ForeName><Initials>JS</Initials><AffiliationInfo><Affiliation>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Canterbury, Private Bag 4800, Christchurch, 8041, New Zealand.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Kruger</LastName><ForeName>Paul E</ForeName><Initials>PE</Initials><Identifier Source="ORCID">http://orcid.org/0000-0003-4847-6780</Identifier><AffiliationInfo><Affiliation>Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Canterbury, Private Bag 4800, Christchurch, 8041, New Zealand.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Chastanet</LastName><ForeName>Guillaume</ForeName><Initials>G</Initials><AffiliationInfo><Affiliation>CNRS, Université de Bordeaux, ICMCB, 87 avenue du Dr. A. Schweitzer, Pessac, 33608, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Murray</LastName><ForeName>Keith S</ForeName><Initials>KS</Initials><Identifier Source="ORCID">http://orcid.org/0000-0003-4098-9389</Identifier><AffiliationInfo><Affiliation>School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.</Affiliation></AffiliationInfo></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2017</Year><Month>05</Month><Day>05</Day></ArticleDate></Article><MedlineJournalInfo><Country>Germany</Country><MedlineTA>Chemistry</MedlineTA><NlmUniqueID>9513783</NlmUniqueID><ISSNLinking>0947-6539</ISSNLinking></MedlineJournalInfo><KeywordList Owner="NOTNLM"><Keyword MajorTopicYN="N">Schiff base ligands</Keyword><Keyword MajorTopicYN="N">halogen bonding</Keyword><Keyword MajorTopicYN="N">intermolecular interactions</Keyword><Keyword MajorTopicYN="N">iron complexes</Keyword><Keyword MajorTopicYN="N">spin crossover</Keyword></KeywordList></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="received"><Year>2017</Year><Month>01</Month><Day>16</Day></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2017</Year><Month>5</Month><Day>6</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2017</Year><Month>5</Month><Day>6</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2017</Year><Month>5</Month><Day>6</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">28474778</ArticleId><ArticleId IdType="doi">10.1002/chem.201700232</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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