Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 39, Pages 11457-11461Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201505781
Keywords
alkenes; metal-ligand interactions; molecular motors; photochromism; ruthenium
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Funding
- The Netherlands Organization for Scientific Research (NWO-CW)
- Ministry of Education, Culture and Science [024.001.035]
- European Research Council (Advanced Investigator Grant) [227897]
- The Netherlands Organization for Scientific Research (Veni grant)
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Toward the development of visible-light-driven molecular rotary motors, an overcrowded alkene-based ligand and the corresponding ruthenium(II) complex is presented. In our design, a 4,5-diazafluorenyl coordination motif is directly integrated into the motor function. The photochemical and thermal isomerization behavior has been studied by UV/Vis and NMR spectroscopy. Upon coordination to a Ru-II bipyridine complex, the photoisomerization process can be driven by visible (lambda(max) = 450 nm) instead of UV light and furthermore, a large increase of the speed of rotation is noted. DFT calculations point to a contraction of the diaza-fluorenyl lower half upon metal-coordination resulting in reduced steric hindrance in the fjord region of the molecule. Consequently, it is shown that metal-ligand interactions can play an important role in the adjustment of both photophysical and thermodynamic properties of molecular motors.
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