Multistate Dihydroazulene-Spiropyran Dyads: Path-Dependent Switchings and Refinement of the "Meta-rule" of Photoactivity.

Multistate switches are interesting systems for a plethora of potential applications, such as for data storage involving many different states or for logic operations characterized by specific outputs. The main challenge is to achieve a precise control of accessibility to a specific state via a given sequence of multiple stimuli. Here, we have connected dihydroazulene (DHA) and spiropyran (SP) photoswitches in dyads to elucidate differences in optical and switching properties between ortho-, meta-, and para-phenylene-bridged dyads. Dyads were prepared by Suzuki and Sonogashira coupling reactions and photoisomerizations studied in detail by stationary and ultrafast spectroscopies. Moreover, the kinetics of thermal back-reactions of meta-stable states were studied. The results show path-dependent switchings of the dyads using light in combination with other stimuli (acid/base/heat), allowing access to eight distinct states. The accessibility to some specific states via only one sequence of external stimuli provides an additional degree of data storage-information is not only stored as the state itself but also as the unique sequence of stimuli required to reach this state. By changing the bridging unit between the photoswitches, various properties (outputs) were finely tuned such as absorption and fluorescence behaviors, lifetime of meta-stable state, and photoisomerization dynamics.