Hardy Matthias, Tessarolo Jacopo, Holstein Julian J, Struch Niklas, Wagner Norbert, Weisbarth Ralf, Engeser Marianne, Beck Johannes, Horiuchi Shinnosuke, Clever Guido H, Lützen Arne
Rheinische Friedrich-Wilhelms-Universität Bonn, Kekulé-Institut für Organische Chemie und Biochemie, Gerhard-Domagk-Str. 1, 53121, Bonn, Germany.
Current address: BASF SE, Speyerer Str. 2, 67117, Limburgerhof, Germany.
Angew Chem Int Ed Engl. 2021 Oct 4;60(41):22562-22569. doi: 10.1002/anie.202108792. Epub 2021 Sep 6.
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 Pt -cubes and their corresponding Zn Pt 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 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.
使用4-(4'-吡啶基)苯胺作为简单有机结构单元,与三种不同的醛组分以及金属(II)盐相结合,通过亚组分自组装方法得到了三种不同的铁铂立方体及其相应的锌铂类似物。使用锌(II)盐产生抗磁性笼,而铁(II)盐产生在溶液中表现出自旋交叉行为的金属超分子笼。自旋转变温度T取决于所引入的醛组分,为有意合成具有定制转变特性的自旋交叉化合物提供了一个构建工具包。引入4-噻唑甲醛或N-甲基-2-咪唑甲醛得到在室温左右发生自旋交叉的笼,而使用1H-4-咪唑甲醛得到的笼在低温下表现出自旋转变。通过同步辐射X射线衍射对三种新结构进行了表征,所有结构均通过质谱、核磁共振和紫外/可见光谱进行了表征。