Ordered photo- and electroactive thin polymer layers

[Display omitted] •Photo- and electroactive polymer brushes and polyelectrolyte multilayer films are reviewed.•Concepts of micellar polyelectrolyte multilayers and template polymerization of conjugated polymer brushes are introduced.•Influence of ordering in thin polymer layers on directional energy or electron transfer is discussed. Photo- and electroactive nanometer scale thin films are of growing importance in applications related to solar energy conversion. Properly ordered surface-tethered polymer layers may mimic performance of natural photosynthetic systems serving as platforms for light harvesting, directional energy and electron transfer in confined environments. Herein we review selected polymer photo- and electroactive systems and propose novel approaches for obtaining polymer layers with spatially ordered arrays of chromophores and/or electroactive chains. Specifically, the use of amphiphilic polyelectrolyte micelles in layer-by-layer (LbL) electrostatic self-assembly was shown as an efficient way to incorporate non-aggregated dyes into the multilayer films. The synthesis of conjugated polymer brushes via self-templating surface-initiated polymerization (ST-SIP) was demonstrated as a versatile route toward ordered 1D molecular wires. Such ordered structures realized in LbL films or polymer brushes would be beneficial for applications requiring directional transport of excitation energy and electrons on macromolecular scale that should be realized in ultimate devices for solar energy conversion.