Premium
Enantiomerically Pure [M 6 L 12 ] or [M 12 L 24 ] Polyhedra from Flexible Bis(Pyridine) Ligands
Author(s) -
Gütz Christoph,
Hovorka Rainer,
Klein Christoph,
Jiang QianQian,
Bannwarth Christoph,
Engeser Marianne,
Schmuck Carsten,
Assenmacher Wilfried,
Mader Werner,
Topić Filip,
Rissanen Kari,
Grimme Stefan,
Lützen Arne
Publication year - 2014
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.201308651
Subject(s) - polyhedron , self assembly , pyridine , chemistry , crystallography , hexa , aryl , ion , stereochemistry , combinatorics , organic chemistry , alkyl , mathematics
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.