Desymmetrization of an octahedral coordination complex Inside a self-assembled exoskeleton

Johnstone, Mark, Schwarze, Eike K, Ahrens, Jennifer, Schwarzer, Dirk, Holstein, Julian J, Dittrich, Birger, Pfeffer, Frederick and Clever, Guido H 2016, Desymmetrization of an octahedral coordination complex Inside a self-assembled exoskeleton, Chemistry - A european journal, vol. 22, pp. 10791-10795, doi: 10.1002/chem.201602497.

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Title Desymmetrization of an octahedral coordination complex Inside a self-assembled exoskeleton
Author(s) Johnstone, Mark
Schwarze, Eike K
Ahrens, Jennifer
Schwarzer, Dirk
Holstein, Julian J
Dittrich, Birger
Pfeffer, FrederickORCID iD for Pfeffer, Frederick
Clever, Guido H
Journal name Chemistry - A european journal
Volume number 22
Start page 10791
End page 10795
Total pages 5
Publisher Wiley
Place of publication Chichester, Eng
Publication date 2016-06-21
ISSN 0947-6539
Keyword(s) anion recognition
coordination cages
endohedral functionalization
host-guest chemistry
supramolecular chemistry
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Summary 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.
Language eng
DOI 10.1002/chem.201602497
Field of Research 030302 Nanochemistry and Supramolecular Chemistry
030207 Transition Metal Chemistry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
ERA Research output type C Journal article
Copyright notice ©2016, Wiley
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