Dipolar Photosystems: Engineering Oriented Push-Pull Components into Double- and Triple-Channel Surface Architectures

Abstract

Push-pull aromatics are not popular as optoelectronic materials because their supramolecular organization is difficult to control. However, recent progress with synthetic methods has suggested that the directional integration of push-pull components into multicomponent photosystems should become possible. In this study, we report the design, synthesis, and evaluation of double- or triple-channel architectures that contain π stacks with push-pull components in parallel or mixed orientation. Moreover, the parallel push-pull stacks were uniformly oriented with regard to co-axial stacks, either with inward or outward oriented push-pull dipoles. Hole-transporting (p) aminoperylenemonoimides (APIs) and aminonaphthalimides (ANIs) are explored for ordered push-pull stacks. For the co-axial electron-transporting (n) stacks, naphthalenediimides (NDIs) are used. In double-channel photosystems, mixed push-pull stacks are overall less active than parallel push-pull stacks. The orientation of the parallel push-pull stacks with regard to the co-axial NDI stacks has little influence on activity. In triple-channel photosystems, outward-directed dipoles in bridging stacks between peripheral p and central n channels show higher activity than inward-directed dipolar stacks. Higher activities in response to direct irradiation of outward-directed parallel stacks reveal the occurrence of quite remarkable optical gating.

Keywords: dipolar photosystems; disulfide exchange; hydrazone exchange; polymerization; push-pull chromophores.