A pH Activated Configurational Rotary Switch: Controlling the E/Z Isomerization in Hydrazones

作者：Landge Shainaz M; Aprahamian Ivan^*

来源：Journal of the American Chemical Society, 2009, 131(51): 18269-+.

DOI：10.1021/ja909149z

The replacement of one of the carbonyl groups in a 1,2,3-triketone-2-naphthylhydrazone with a pyridine ring yields an original molecular switch that can be switched fully, effectively, and reversibly between the E and Z configurations. This hydrazone-based, pH-controlled, molecular switch is the first example of a chemically controlled configurational rotary switch. The bistable switch exists primarily (97%) as the E configuration in solution and can be converted quantitatively to the Z-H(+) configuration upon treatment with trifluoroacetic acid. When Z-H(+) is passed over a plug of K(2)CO(3), the "metastable" Z configuration is observed using (1)H NMR spectroscopy, which thermally equilibrates to give back the E configuration. The rate of this process is dependent on the polarity of the solvent, indicating that the E/Z isomerization takes place via a rotation around the hydrazone C=N bond.

• 出版日期2009-12-30