Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach
Jiangkun Ouyang, Anne Swartjes, Marc Geerts, Pieter J. Gilissen, Danni Wang, Paula C. P. Teeuwen, Paul Tinnemans, Nicolas Vanthuyne, Sara Chentouf, Floris P. J. T. Rutjes, Jean‐Valère Naubron, Jeanne Crassous, Johannes A. A. W. Elemans, Roeland J. M. Nolte
Abstract
Porphyrin cage-compounds are used as biomimetic models and substrate-selective catalysts in supramolecular chemistry. In this work we present the resolution of planar-chiral porphyrin cages and the determination of their absolute configuration by vibrational circular dichroism in combination with density functional theory calculations. The chiral porphyrin-cages form complexes with achiral and chiral viologen-guests and upon binding one of the axial enantiomorphs of the guest is bound selectively, as is indicated by induced-electronic-dichroism-spectra in combination with calculations. This host-guest binding also leads to unusual enhanced vibrational circular dichroism, which is the result of a combination of phenomena, such as rigidification of the host and guest structures, charge transfer, and coupling of specific vibration modes of the host and guest. The results offer insights in how the porphyrin cage-compounds may be used to construct a future molecular Turing machine that can write chiral information onto polymer chains.