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Enantiomerically Pure [M6L12] or [M12L24] Polyhedra from Flexible Bis(Pyridine) Ligands
Authors:Dr. Christoph Gütz  Dipl.‐Chem. Rainer Hovorka  M. Sc. Christoph Klein  M. Sc. Qian‐Qian Jiang  M. Sc. Christoph Bannwarth  Dr. Marianne Engeser  Prof. Dr. Carsten Schmuck  Dr. Wilfried Assenmacher  Prof. Dr. Werner Mader  M. Sc. Filip Topić  Prof. Dr. Kari Rissanen  Prof. Dr. Stefan Grimme  Prof. Dr. Arne Lützen
Affiliation:1. Kekulé‐Institut für Organische Chemie und Biochemie, Universit?t Bonn, Gerhard‐Domagk‐Str. 1, 53121 Bonn (Germany);2. Institut für Organische Chemie, Universit?t Duisburg‐Essen, Universit?tsstr. 7, 45117 Essen (Germany);3. Mulliken Center for Theoretical Chemistry, Universit?t Bonn, Beringstr. 4, 53115 Bonn (Germany);4. Institut für Anorganische Chemie, Universit?t Bonn, R?merstr. 164, 53117 Bonn (Germany);5. Department of Chemistry, Nanoscience Center, University of Jyv?skyl? (Finland)
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 PdII 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.
Keywords:CD spectroscopy  DFT calculations  metallosupramolecular chemistry  self‐assembly  self‐sorting
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