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Multi-photochromic systems incorporating individually addressable switching units are attractive for development of advanced data storage devices. Here, we present the synthesis and properties of a selection of such molecular systems incorporating the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch. The influence of the linker (meta-phenylene vs. azulene-1,3-diyl vs. thiophene-2,5-diyl) separating two DHA units on the switching properties was investigated. An azulene-1,3-diyl spacer largely inhibited both the DHA-to-VHF photoisomerizations and the thermal VHF-to-DHA back-reactions; the latter occurred ten times slower than for the related compound with a meta-phenylene spacer. A DHA trimer containing three DHA units around a central benzene ring was found to undergo stepwise DHA-to-VHF photoisomerizations, whereas the thermal back-reactions occurred at similar rates for the three VHF entities. A meta-phenylene-bridged DHA dimer was subjected to further structural modifications at position C-1 of each DHA, having strong implications for the switching events, and synthetic steps for further functionalizations at position C-7 of each DHA were investigated. Finally, the molecular structure (from X-ray crystallographic analysis) between the meta-phenylene-bridged DHA dimer and CuI is presented.

A theoretical and experimental investigation of conformational modifications on the thermodynamic, optical, and switching properties of dihydroazulene/vinylheptafulvene (DHA/VHF) photoswitches, in the context of molecular solar thermal (MOST) systems, is described herein. The optical properties of monomeric DHA/VHF systems are found to be strongly dependent on structural changes which can be tuned via steric modifications. This correlation is then used to infer structural features of more complex, macrocyclic DHA/VHF systems based on their optical properties. The introduction of macrocyclic ring strain is furthermore found to significantly influence the switching behavior of DHA/VHF moieties compared to non-cyclized systems. The thermal ring closure of macrocyclic VHF-VHF systems is found to occur in a stepwise manner, enabling the release of the energy on both a fast and slow timescale, hypothetically addressing both immediate and long-term energy discharge requirements. The incorporation of an azobenzene (AZB) moiety in a macrocyclic system imparts higher rigidity compared to analogs including alkyl chains, indicating increased ring strain in the ground (DHA-DHA) state relative to the metastable (VHF-VHF) state. The AZB is then shown to function as an orthogonal switch to trigger energy release from the metastable to the ground state, enhancing the reaction 3-fold. Lastly, the multimode switching potential of several ruthenium alkynyl DHA ([Ru*]-DHA) systems is elucidated through a variety of spectroelectrochemical techniques demonstrating, for one analog, complete six-state switching behavior.