Desymmetrization of an octahedral coordination complex Inside a self-assembled exoskeleton
Data(s) |
21/06/2016
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Resumo |
The synthesis of a centrally functionalized, ribbon-shaped [6]polynorbornane ligand L that self-assembles with PdII cations into a (Pd2L4) coordination cage is reported. The shape-persistent (Pd2L4) cage contains two axial cationic centers and an array of four equatorial H-bond donors pointing directly towards the center of the cavity. This precisely defined supramolecular environment is complementary to the geometry of classic octahedral complexes [M(XY)6] with six diatomic ligands. Very strong binding of [Pt(CN)6]2- to the cage was observed, with the structure of the host-guest complex ([Pt(CN)6]@Pd2L4) supported by NMR spectroscopy, MS, and X-ray data. The self-assembled shell imprints its geometry on the encapsulated guest, and desymmetrization of the octahedral platinum species by the influence of the D4h-symmetric second coordination sphere was evidenced by IR spectroscopy. [Fe(CN)6]3- and square-planar [Pt(CN)4]2- were strongly bound. Smaller octahedral anions such as [SiF6]2-, neutral carbonyl complexes ([M(CO)6]; M=Cr, Mo, W) and the linear [Ag(CN)2]- anion were only weakly bound, showing that both size and charge match are key factors for high-affinity binding. |
Identificador | |
Idioma(s) |
eng |
Publicador |
Wiley |
Relação |
http://dro.deakin.edu.au/eserv/DU:30085152/johnstone-desymmetrization-2016.pdf http://www.dx.doi.org/10.1002/chem.201602497 |
Direitos |
2016, Wiley |
Palavras-Chave | #anion recognition #coordination cages #endohedral functionalization #host-guest chemistry #supramolecular chemistry #Science & Technology #Physical Sciences #Chemistry, Multidisciplinary #Chemistry #METAL-ORGANIC CAGES #CANCER-CELLS #LIGANDS #CYCLOADDITION #ENCAPSULATION #DISTORTIONS #INCLUSION #DELIVERY #CLICK |
Tipo |
Journal Article |