INOR 410 |
| Redox-driven molecular switches form a basis for the development of electronic devices at the nanoscale. Potential examples include mixed-valent (MV) compounds characterized by two metal moieties coupled together by a bridging ligand. The Cu(I) polypyridines are not common MV systems on account of their bistable stereoelectronic preferences switching from 4- to 5-coordinate, for Cu(I) and Cu(II), respectively. Consequently, we are employing the mechanical bond to maintain the integrity of the MV states to facilitate their characterization. To this end, [2]- and [3]pseudorotaxanes of the bridging ligand 3,6-bis(2-pyridyl-5-methyl)-1,2,4,5-tetrazine (diMe-BPTZ) threaded by two phenanthroline-based macrocycles have been developed. Dynamic complex formation was confirmed using mass spectrometry, NMR and UV-Vis-NIR spectroscopy. The optical properties display absorptions out to 1100 nm, belying a rich electronic structure, which is supported by a mixed-valent signature in the electrochemistry. These studies bode well for the preparation and characterization of the corresponding MV [3]rotaxanes. |
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Mixed Valency in Chemistry
2:00 PM-5:20 PM, Monday, August 20, 2007 BCEC -- 205B, Oral
Division of Inorganic Chemistry |