By G. W. Series
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Extra info for Spectrum of Atomic Hydrogen
20) is approximately 25 kcal mol)1, and that rotation occurs equally in both directions when thermal energy is applied to the system; that is, the molecular system works more as a brake than a ratchet. The essence of converting 37b into a molecular motor involves continuing the frictionbraking action to prevent counterclockwise rotation, while using the chemical energy of phosgene to harvest ambient thermal energy, thereby selectively fostering clockwise rotation of the triptycene rotor. The basic strategy to produce the unidirectional rotation is presented in detail in Fig.
Variable-temperature 1H NMR experiments (see Figs. 10 and 11) document the engagement of the brake. In particular, at )30 °C, and in contrast to the system without any metal ion, the three aromatic rings of the triptycene are no longer equivalent because of the arrest of rotation on the NMR time scale. That nonequivalence is most clearly seen (Fig. 53 (in a 2:1 ratio) due to the two Ha and one Ha¢ resonances in Fig. 11d indicating that engagement of the brake results in the plane of symmetry implied in 35.
Over 2000 years later, Iwamura and co-workers succeeded in synthesizing a chemical gear train (see Fig. 4) , a system consisting of two labeled triptycenes connected by ether-type bonds (7). The movement is more complex in these systems. The rotation follows a rule, which is that the motion of the two terminal gears in a train is disrotarory if the number of gears is even and conrotatory if the number is odd. As with the meso and d/l forms of 1±6, substituted derivatives of phase isomers 7 can be separated by HPLC and identi®ed by NMR.