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Catenation and Aggregation of Multi-Cavity Coordination Cages.

Authors :: Zhu R
Regeni I
Holstein JJ
Dittrich B
Simon M
Prévost S
Gradzielski M
Clever GH
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2018 Oct 08; Vol. 57 (41), pp. 13652-13656. Date of Electronic Publication: 2018 Jul 26.
Publication Year :: 2018
Abstract: A series of metal-mediated cages, having multiple cavities, was synthesized from Pd <superscript>II</superscript> cations and tris- or tetrakis-monodentate bridging ligands and characterized by NMR spectroscopy, mass spectrometry, and X-ray methods. The peanut-shaped [Pd <subscript>3</subscript> L <superscript>1</superscript> <subscript>4</subscript> ] cage deriving from the tris-monodentate ligand L <superscript>1</superscript> could be quantitatively converted into its interpenetrated [5Cl@Pd <subscript>6</subscript> L <superscript>1</superscript> <subscript>8</subscript> ] dimer featuring a linear {[Pd-Cl-] <subscript>5</subscript> Pd} stack as an unprecedented structural motif upon addition of chloride anions. Small-angle neutron scattering (SANS) experiments showed that the cigar-shaped assembly with a length of 3.7 nm aggregates into mono-layered discs of 14 nm diameter via solvophobic interactions between the hexyl sidechains. The hepta-cationic [5Cl@Pd <subscript>6</subscript> L <superscript>1</superscript> <subscript>8</subscript> ] cage was found to interact with polyanionic oligonucleotide double-strands under dissolution of the aggregates in water, rendering the compound class interesting for applications based on non-covalent DNA binding.<br /> (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)