Dynamic Complex-to-Complex Transformations of Heterobimetallic Systems Influence the Cage Structure or Spin State of Iron(II) Ions.,Angewandte Chemie International Edition

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Dynamic Complex-to-Complex Transformations of Heterobimetallic Systems Influence the Cage Structure or Spin State of Iron(II) Ions.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-01-09 , DOI: 10.1002/anie.201914629
Matthias Hardy ₁ , Niklas Struch _{1,

2} , Julian J Holstein ₃ , Gregor Schnakenburg ₄ , Norbert Wagner ₄ , Marianne Engeser ₁ , Johannes Beck ₄ , Guido H Clever ₃ , Arne Lützen ₁

Affiliation

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.

中文翻译：

异双金属系统的复杂的复合物动态转变影响笼形结构或铁离子的自旋态。

采用分子库方法，使用铁（II）和钯（II）构件，从同一单核金属配体组装了两个新的异双金属笼，分别是三角双锥体和立方。配体系统设计为易于通过子组件自组装进行组装。它允许在铁（II）中心引入空间应变，从而稳定了其顺磁性高自旋状态。该空间应变被用来驱动金属配体和异双金属笼的动态复合物到复合物的转变。由于化学刺激而增加了空间上较不拥挤的子组件，从而使所有复合物转化为先前报道的低旋转类似物。金属配位体和双锥体比立方笼更容易结合新的构建基块，可能是因为空间上拥挤的金属配体的几何结构有利于立方体的形成。此外，有可能在添加更有利的螯合配体后引发结构转变，将立方结构转变为双锥体结构。

更新日期：2020-01-10

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