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

Angewandte Chemie / International edition 60(41), 22562 - 22569 (2021). doi:10.1002/anie.202108792
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 Fe8Pt6-cubes and their corresponding Zn$_8$Pt$_6$ 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 T$_{1/2}$ 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 N-methyl-2-imidazole-carbaldehyde yielded cages that undergo spin-crossover around room temperature whereas the cage obtained using 1H-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.
Published by Wiley-VCH, Weinheim