Enantiomerically pure [M(6)L(12)] or [M(12)L(24)] polyhedra from flexible bis(pyridine) ligands.
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.
Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn (Germany).
Christoph
C
Gütz
Rainer
R
Hovorka
Christoph
C
Klein
Qian-Qian
QQ
Jiang
Christoph
C
Bannwarth
Marianne
M
Engeser
Carsten
C
Schmuck
Wilfried
W
Assenmacher
Werner
W
Mader
Filip
F
Topić
Kari
K
Rissanen
Stefan
S
Grimme
Arne
A
Lützen
CD spectroscopy; DFT calculations; metallosupramolecular chemistry; self-assembly; self-sorting