A Rotaxane‐like Cage‐in‐Ring Structural Motif for a Metallosupramolecular Pd6L12 Aggregate

A BODIPY‐based bis(3‐pyridyl) ligand undergoes self‐assembly upon coordination to tetravalent palladium(II) cations to form a Pd6L12 metallosupramolecular assembly with an unprecedented structural motif that resembles a rotaxane‐like cage‐in‐ring arrangement. In this assembly the ligand adopts two d...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-09, Vol.57 (37), p.12171-12175
Main Authors: Käseborn, Matthias, Holstein, Julian J., Clever, Guido H., Lützen, Arne
Format: Article
Language:English
Subjects:
Assembly
BODIPY
Cages
Catenation
Cations
Chromophores
Conformation
Crystallography
Ligands
Magnetic resonance spectroscopy
Mass spectrometry
Mass spectroscopy
metallosupramolecular chemistry
NMR spectroscopy
Palladium
palladium complexes
self-assembly
Shafts (machine elements)
π-π-interactions
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Summary:A BODIPY‐based bis(3‐pyridyl) ligand undergoes self‐assembly upon coordination to tetravalent palladium(II) cations to form a Pd6L12 metallosupramolecular assembly with an unprecedented structural motif that resembles a rotaxane‐like cage‐in‐ring arrangement. In this assembly the ligand adopts two different conformations—a C‐shaped one to form a Pd2L4 cage which is located in the center of a Pd4L8 ring consisting of ligands in a W‐shaped conformation. This assembly is not mechanically interlocked in the sense of catenation but it is stabilized only by attractive π‐stacking between the peripheral BODIPY chromophores and the ligands’ skeleton as well as attractive van der Waals interactions between the long alkoxy chains. As a result, the co‐arrangement of the two components leads to a very efficient space filling. The overall structure can be described as a rotaxane‐like assembly with a metallosupramolecular cage forming the axle in a metallosupramolecular ring. This unique structural motif could be characterized via ESI mass spectrometry, NMR spectroscopy, and X‐ray crystallography. First the cage, then the ring: A BODIPY‐based bis(3‐pyridyl) ligand undergoes self‐assembly upon coordination to tetravalent palladium(II) cations to form a Pd6L12 metallosupramolecular assembly with an unprecedented structural motif that resembles a rotaxane‐like cage‐in‐ring arrangement. This assembly is not mechanically interlocked in the sense of a catenation but it is stabilized only by attractive noncovalent interactions.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201806814