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Updated: May 3, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Enantiomerically pure [M(6)L(12)] or [M(12)L(24)] polyhedra from flexible bis(pyridine) ligands
Christoph Gütz1, Rainer Hovorka, Christoph Klein
1Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn (Germany).
Abstract:
Coordination-driven self-assembly is one of the most powerful strategies to prepare nanometer-sized discrete (supra)molecular assemblies. Herein, we report on the use of two constitutionally isomeric BINOL-based bis(pyridine) ligands for this purpose. Upon coordination to Pd(II) ions these self-assemble into enantiomerically pure endo- and exo-functionalized hexa- and dodecanuclear metallosupramolecular spheres with a chiral skeleton depending on the substitution pattern of the BINOL core. These aggregates were characterized by NMR, MS, DLS, TEM, and EELS as well as ECD. Furthermore, experimental ECD data could be compared to those obtained from theoretical simulations using a simplified Tamm-Dancoff approximation to time-dependent DFT to rationalize the extraordinary high molar circular dichroisms. Despite the rotational freedom around the central aryl-aryl bond of these ligands, the self-assembly process happens completely selective in a "narcissistic" self-recognition manner.
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