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Catenation and Aggregation of Multi‐Cavity Coordination Cages
Author(s) -
Zhu Rongmei,
Regeni Irene,
Holstein Julian J.,
Dittrich Birger,
Simon Miriam,
Prévost Sylvain,
Gradzielski Michael,
Clever Guido H.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201806047
Subject(s) - chemistry , solvophobic , crystallography , dimer , denticity , cationic polymerization , supramolecular chemistry , solvent , polymer chemistry , crystal structure , organic chemistry
A series of metal‐mediated cages, having multiple cavities, was synthesized from Pd II cations and tris‐ or tetrakis‐monodentate bridging ligands and characterized by NMR spectroscopy, mass spectrometry, and X‐ray methods. The peanut‐shaped [Pd 3 L 1 4 ] cage deriving from the tris‐monodentate ligand L 1 could be quantitatively converted into its interpenetrated [5Cl@Pd 6 L 1 8 ] dimer featuring a linear {[Pd‐Cl‐] 5 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 6 L 1 8 ] 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.

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