A Family of Heterobimetallic Cubes Shows Spin‐Crossover Behaviour Near Room Temperature

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  • Matthias Hardy
    Rheinische Friedrich-Wilhelms-Universität Bonn Kekulé-Institut für Organische Chemie und Biochemie Gerhard-Domagk-Str. 1 53121 Bonn Germany
  • Jacopo Tessarolo
    Technische Universität Dortmund Otto-Hahn-Str. 6 44227 Dortmund Germany
  • Julian J. Holstein
    Technische Universität Dortmund Otto-Hahn-Str. 6 44227 Dortmund Germany
  • Niklas Struch
    Rheinische Friedrich-Wilhelms-Universität Bonn Kekulé-Institut für Organische Chemie und Biochemie Gerhard-Domagk-Str. 1 53121 Bonn Germany
  • Norbert Wagner
    Rheinische Friedrich-Wilhelms-Universität Bonn Institut für Anorganische Chemie Gerhard-Domagk-Str. 1 53121 Bonn Germany
  • Ralf Weisbarth
    Rheinische Friedrich-Wilhelms-Universität Bonn Institut für Anorganische Chemie Gerhard-Domagk-Str. 1 53121 Bonn Germany
  • Marianne Engeser
    Rheinische Friedrich-Wilhelms-Universität Bonn Kekulé-Institut für Organische Chemie und Biochemie Gerhard-Domagk-Str. 1 53121 Bonn Germany
  • Johannes Beck
    Rheinische Friedrich-Wilhelms-Universität Bonn Institut für Anorganische Chemie Gerhard-Domagk-Str. 1 53121 Bonn Germany
  • Shinnosuke Horiuchi
    Technische Universität Dortmund Otto-Hahn-Str. 6 44227 Dortmund Germany
  • Guido H. Clever
    Technische Universität Dortmund Otto-Hahn-Str. 6 44227 Dortmund Germany
  • Arne Lützen
    Rheinische Friedrich-Wilhelms-Universität Bonn Kekulé-Institut für Organische Chemie und Biochemie Gerhard-Domagk-Str. 1 53121 Bonn Germany

Abstract

<jats:title>Abstract</jats:title><jats:p>Using 4‐(4′‐pyridyl)aniline as a simple organic building block in combination with three different aldehyde components together with metal(II) salts gave three different Fe<jats:sub>8</jats:sub>Pt<jats:sub>6</jats:sub>‐cubes and their corresponding Zn<jats:sub>8</jats:sub>Pt<jats:sub>6</jats:sub> analogues by employing the subcomponent self‐assembly approach. Whereas the use of zinc(II) salts gave rise to diamagnetic cages, iron(II) salts yielded metallosupramolecular cages that show spin‐crossover behaviour in solution. The spin‐transition temperature <jats:italic>T</jats:italic><jats:sub>1/2</jats:sub> depends on the incorporated aldehyde component, giving a construction kit for the deliberate synthesis of spin‐crossover compounds with tailored transition properties. Incorporation of 4‐thiazolecarbaldehyde or <jats:italic>N</jats:italic>‐methyl‐2‐imidazole‐carbaldehyde yielded cages that undergo spin‐crossover around room temperature whereas the cage obtained using 1<jats:italic>H</jats:italic>‐4‐imidazolecarbaldehyde shows a spin‐transition at low temperatures. Three new structures were characterized by synchrotron X‐ray diffraction and all structures were characterized by mass spectrometry, NMR and UV/Vis spectroscopy.</jats:p>

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