Surface-Photoactive Substrate Interactions

The competition between molecular-based and molecule-substrate interactions is one of the features that make supramolecular assemblies based on the combination of molecular components and solid substrates so exciting and also potentially useful from the applications point of view. The control issue is whether can one achieve long-lived charge separation between molecular components when immobilized on a surface, and from the fundamental perspective, can the interactions between the surface and molecular components be manipulated In this section, the immobilization of molecular components consisting of at least two electroactive and/or photoactive units will be discussed. The intramolecular interactions within these dyads in solution, as well as their behavior as interfacial supramolecular triads when immobilized on nanocrystalline TiC>2, will be compared. 

In a more general sense, these observations show that upon immobilization of photoactive compounds onto a solid substrate a substantial difference is detected between the photophysical processes observed for the heterotriad and the dyad in solution. More importantly, direct injection from those moieties not directly bound to the oxide surface can be efficient - this is always fully realized and such an observation is important for the further development of real devices. As a result of this through-space interaction, no osmium-based emission is observed and injection from both the ruthenium and the osmium centers is faster than the laser pulse. An interesting observation is also that upon irradiation of the heterotriad Ti02-Ru-0s, only one final product, i.e. Ti02(e)-Ru(ll)0s(lll), is obtained. In view of the potential of these modified surfaces as potential molecular devices, this is an important feature. The presence of a rigid structure rather than a flexible one, as observed in the Ru-Rh case, clearly leads to a more uniform behavior. 

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