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Desymmetrization of an Octahedral Coordination Complex Inside a Self-Assembled Exoskeleton

Version 2 2024-06-04, 02:49
Version 1 2016-07-29, 15:05
journal contribution
posted on 2024-06-04, 02:49 authored by MD Johnstone, EK Schwarze, J Ahrens, D Schwarzer, JJ Holstein, B Dittrich, Fred PfefferFred Pfeffer, GH Clever
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.

History

Journal

Chemistry - A European Journal

Volume

22

Pagination

10791-10795

Location

Germany

ISSN

0947-6539

eISSN

1521-3765

Language

English

Publication classification

C Journal article, C1 Refereed article in a scholarly journal

Copyright notice

2016, Wiley

Issue

31

Publisher

WILEY-V C H VERLAG GMBH