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  Desymmetrization of an octahedral coordination complex inside a self-assembled exoskeleton.

Johnstone, M. D., Schwarze, E. K., Ahrens, J., Schwarzer, D., Holstein, J. J., Dittrich, B., et al. (2016). Desymmetrization of an octahedral coordination complex inside a self-assembled exoskeleton. Chemistry - A European Journal, 22(31), 10791-10795. doi:10.1002/chem.201602497.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002B-82EB-A Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002C-C5D1-0
Genre: Journal Article

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 Creators:
Johnstone, M. D., Author
Schwarze, E. K., Author
Ahrens, J.1, Author              
Schwarzer, D.2, Author              
Holstein, J. J., Author
Dittrich, B., Author
Pfeffer, F. M., Author
Clever, G. H., Author
Affiliations:
1Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_578600              
2Research Group of Reaction Dynamics, MPI for biophysical chemistry, Max Planck Society, ou_578601              

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Free keywords: Anion recognition; Coordination cages; Endohedral functionalization; Host-guest chemistry; Supramolecular chemistry
 Abstract: The synthesis of a centrally functionalized, ribbon-shaped [6]polynorbornane ligand L that self-assembles with Pd(II) cations into a {Pd2 L4 } coordination cage is reported. The shape-persistent {Pd2 L4 } 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 ]@Pd2 L4 } 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.

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Language(s): eng - English
 Dates: 2016-06-212016-07-25
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1002/chem.201602497
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Title: Chemistry - A European Journal
Source Genre: Journal
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Pages: - Volume / Issue: 22 (31) Sequence Number: - Start / End Page: 10791 - 10795 Identifier: -