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Halogen Substitution Effects on N2 O Schiff Base Ligands in Unprecedented Abrupt FeII Spin Crossover Complexes.
Phonsri, Wasinee; Macedo, David S; Vignesh, Kuduva R; Rajaraman, Gopalan; Davies, Casey G; Jameson, Guy N L; Moubaraki, Boujemaa; Ward, Jas S; Kruger, Paul E; Chastanet, Guillaume; Murray, Keith S.
Afiliação
  • Phonsri W; School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.
  • Macedo DS; School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.
  • Vignesh KR; IITB-Monash Research Academy, IIT Bombay, Mumbai, 400076, India.
  • Rajaraman G; Department of Chemistry, Indian Institute of Technology, Mumbai, 400076, India.
  • Davies CG; Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Otago, Dunedin, 9054, New Zealand.
  • Jameson GNL; Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Otago, Dunedin, 9054, New Zealand.
  • Moubaraki B; School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.
  • Ward JS; Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Canterbury, Private Bag 4800, Christchurch, 8041, New Zealand.
  • Kruger PE; Department of Chemistry, MacDiarmid Institute for Advanced, Materials and Nanotechnology, University of Canterbury, Private Bag 4800, Christchurch, 8041, New Zealand.
  • Chastanet G; CNRS, Université de Bordeaux, ICMCB, 87 avenue du Dr. A. Schweitzer, Pessac, 33608, France.
  • Murray KS; School of Chemistry, Building 23, Monash University, Clayton, Victoria, 3800, Australia.
Chemistry ; 23(29): 7052-7065, 2017 May 23.
Article em En | MEDLINE | ID: mdl-28474778
A family of halogen-substituted Schiff base iron(II) complexes, [FeII (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 FeII N/O species. We have recently reported subtle symmetry breaking in [FeII (qsal-Cl)2 ] 2 with two spin transition steps occurring at 308 and 316 K. A photomagnetic study reveals almost full HS conversion of [FeII (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 [FeII (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, [FeIII (qsal-X)2 ]+ , the two extra π-π and P4AE interactions found in [FeII (qsal-X)2 ] compounds, are believed to be accountable for the spin transitions occurring at ambient temperatures.
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2017 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2017 Tipo de documento: Article