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 language | English |
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Pages (from-to) | 17672-17685 |
Number of pages | 14 |
Journal | Journal of the American Chemical Society |
Volume | 127 |
Issue number | 50 |
DOIs | |
Publication status | Published - 2005 Dec 21 |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry