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Dynamic Complex‐to‐Complex Transformations of Heterobimetallic Systems Influence the Cage Structure or Spin State of Iron(II) Ions
Author(s) -
Hardy Matthias,
Struch Niklas,
Holstein Julian J.,
Schnakenburg Gregor,
Wagner Norbert,
Engeser Marianne,
Beck Johannes,
Clever Guido H.,
Lützen Arne
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201914629
Subject(s) - steric effects , chemistry , trigonal bipyramidal molecular geometry , crystallography , bipyramid , ligand (biochemistry) , stereochemistry , cage , pentagonal bipyramidal molecular geometry , ion , crystal structure , organic chemistry , receptor , biochemistry , mathematics , combinatorics
Two new heterobimetallic cages, a trigonal‐bipyramidal and a cubic one, were assembled from the same mononuclear metalloligand by adopting the molecular library approach, using iron(II) and palladium(II) building blocks. The ligand system was designed to readily assemble through subcomponent self‐assembly. It allowed the introduction of steric strain at the iron(II) centres, which stabilizes its paramagnetic high‐spin state. This steric strain was utilized to drive dynamic complex‐to‐complex transformations with both the metalloligand and heterobimetallic cages. Addition of sterically less crowded subcomponents as a chemical stimulus transformed all complexes to their previously reported low‐spin analogues. The metalloligand and bipyramid incorporated the new building block more readily than the cubic cage, probably because the geometric structure of the sterically crowded metalloligand favours the cube formation. Furthermore it was possible to provoke structural transformations upon addition of more favourable chelating ligands, converting the cubic structures into bipyramidal ones.