Synthesis of chiral self-assembling rhombs and their characterization in solution, in the gas phase, and at the liquid-solid interface

Kyung Seok Jeong, Sun Young Kim, Ueon Sang Shin, Michael Kogej, Nguyen T.M. Hai, Peter Broekmann, Nakcheol Jeong, Barbara Kirchner, Markus Reiher, Christoph A. Schalley

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58 Citations (Scopus)

Abstract

Chiral, enantiopure metallo-supramolecular rhombs self-assemble in solution through coordination of bis-pyridyl-substituted ligands with (en)M(NO 3)2 (en = ethylenediamine, M = PdII, Pt II). Characterization by NMR and CD spectroscopy in solution and by ESI-FT-ICR mass spectrometry in the gas phase suggests that an equilibrium exists in water/methanol of a major 2:2 complex and a minor 3:3 complex of ligands and metal corners. In the gas phase, doubly charged 2:2 complexes fragment into two identical singly charged halves followed by metal-mediated C-H and C-C bond activation reactions within the ethylenediamine ligands. Electrochemical scanning tunneling microscopy (EC-STM) provides in situ imaging of the complexes even with submolecular resolution. Flat-lying rhombs are deposited under potential control from an aqueous electrolyte on a Cu(100) electrode surface precovered by a tetragonal pattern of chloride anions from the supporting electrolyte. Chirality induces the formation of only one domain orientation. Density functional calculations help to interpret the STM images.

Original languageEnglish
Pages (from-to)17672-17685
Number of pages14
JournalJournal of the American Chemical Society
Volume127
Issue number50
DOIs
Publication statusPublished - 2005 Dec 21

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Jeong, K. S., Kim, S. Y., Shin, U. S., Kogej, M., Hai, N. T. M., Broekmann, P., Jeong, N., Kirchner, B., Reiher, M., & Schalley, C. A. (2005). Synthesis of chiral self-assembling rhombs and their characterization in solution, in the gas phase, and at the liquid-solid interface. Journal of the American Chemical Society, 127(50), 17672-17685. https://doi.org/10.1021/ja053781i