Macrocage molecules with a bridged π-electron system have been reported as molecular gyrotops in which the π-electron system can rotate within the cage. We recently reported the dynamics of the rotor in solution using 1,4-naphthalenediyl-bridged molecular gyrotops, which consist of cages formed of three C14, C16, or C18 chains. In this work, we synthesized novel gyrotops with C15 and C17 chains and systematically investigated the activation energies for the rotation of the rotor in solution. The activation energies for rotation in solution were found to decrease with increasing size of the cage. Therefore, a rotational barrier can be designed by adjusting the length of the side chains in these molecular gyrotops. Additionally, these gyrotops were fluorescent in solution; the quantum yields and lifetimes of the fluorescence were investigated. However, these properties were not influenced by the chain length owing to a large difference in time scale between fluorescence (10(-8)-10(-9) s) and the rotational dynamics inside the cage (10°-10(-5) s).

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