Matviyishyn Maksym, A Konieczny Krzysztof, Trzaskowski Bartosz, Szyszko Bartosz
Faculty of Chemistry, University of Wrocław, 14F. Joliot-Curie St., 50-383, Wrocław, Poland.
Department of Chemistry and Biochemistry, University of California, Los Angeles, California, 90024-1569, USA.
Chemistry. 2024 Nov 7;30(62):e202402932. doi: 10.1002/chem.202402932. Epub 2024 Oct 23.
Crownphyrinogens and crownphyrins constitute a group of macrocycles that combine the structural facets of porphyrinoids and crown ethers. The dual-nature cavity embedded in their molecules enables reactivity involving two structurally distinct parts of the macrocyclic ligand. Upon Ni(II) and Pd(II) insertion, coordination compounds are produced wherein the metal is incorporated into the porphyrinoid-like pocket, resulting in monomeric or accordion-like dimeric products, depending on the oxidation level of the macrocycle and metal cation. The reactions with Na(I) and K(I) resulted in the formation of complexes where only the crown ether segment of the molecule is involved in metal binding, yielding remarkable dimeric species. The exploitation of a crownphyrin large enough to accommodate two metal cations allowed the synthesis of an alkali/transition metal binuclear complexes wherein the macrocycle demonstrated the Janus reactivity with one cavity acting as a porphyrinoid and the other mimicking the crown ether.
冠卟啉原和冠卟啉构成了一类大环化合物，它们结合了类卟啉和冠醚的结构特征。其分子中嵌入的双性腔使得大环配体的两个结构不同的部分能够发生反应。在插入Ni(II)和Pd(II)后，会生成配位化合物，其中金属被纳入类卟啉样口袋中，根据大环和金属阳离子的氧化态，会产生单体或手风琴状二聚体产物。与Na(I)和K(I)的反应导致形成仅分子的冠醚部分参与金属结合的配合物，产生了显著的二聚体物种。利用足够大以容纳两个金属阳离子的冠卟啉，使得能够合成碱金属/过渡金属双核配合物，其中大环表现出两面神反应性，一个腔作为类卟啉起作用，另一个模仿冠醚。
