Influencing the self‐sorting behavior of [2.2]paracyclophane based ligands by introducing isostructural binding motifs
Volbach, L., Struch, N., Bohle, F., Topic, F., Schnakenburg, G., Schneider, A., Rissanen, K., Grimme, S., & Lützen, A. (2020). Influencing the self‐sorting behavior of [2.2]paracyclophane based ligands by introducing isostructural binding motifs. Chemistry : A European Journal, 26(15), 3335-3347. https://doi.org/10.1002/chem.201905070
Published inChemistry : A European Journal
© 2019 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
Two isostructural ligands with either nitrile ( L nit ) or isonitrile ( L iso ) moieties directly connected to a [2.2]paracyclophane backbone with pseudo‐meta substitution pattern have been synthesized. The ligand itself ( L nit ) or its precursors ( L iso ) were resolved via HPLC on a chiral stationary phase and the absolute configuration of the isolated enantiomers was assigned by XRD analysis and/or by comparison of quantum‐chemical simulated and experimental ECD‐spectra. Surprisingly, the resulting metallosupramolecular aggregates formed in solution upon coordination of [(dppp)Pd(OTf) 2 ] differ in their composition: whereas L nit forms dinuclear complexes L iso exclusively forms trinuclear ones. Furthermore, they also differ in their chiral self‐sorting behavior as ( rac )‐ L iso undergoes exclusive social self‐sorting leading to a heterochiral assembly whereas ( rac )‐ L iso shows a twofold preference for the formation of homochiral complexes in a narcissistic self‐sorting manner as proven by ESI mass spectrometry and NMR spectroscopy. Interestingly, upon crystallization these discrete aggregates undergo structural transformation to coordination polymers as evidenced by single‐crystal X‐ray diffraction. ...
ISSN Search the Publication Forum0947-6539
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Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Professor, AoF; Research post as Academy Professor, AoF
Additional information about fundingFinancial support from DFG (SFB 813 – Chemistry at Spin Centers) and the Academy of Finland (K.R.: project no’s. 263256, 292746 and 265328) is gratefully acknowledged. N.S. thanks Evonik Foundation for a doctoral scholarship and the DAAD for a travel grant. F. Bohle and S. Grimme gratefully acknowledge financial support by the DFG in the framework of the priority program No. SPP 1807 “Control of Dispersion Interactions in Chemistry”. G.S. thanks Prof. Dr. D. Menche and Prof. Dr. A. C. Filippou for providing X-ray infrastructure. ...
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