Simultaneous control of both the optoelectronic properties and morphology of conjugated polyelectrolytes (CPEs) is a critical requirement for their implementation into high performance organic electronics. Physical interactions (e.g.hydrogen bonding, ionic, p-p stacking) between a CPE and an oppositely charged species can be harnessed to construct hybrid CPE networks with well-defined structural organisation. The challenge, however, is to identify physicochemically compatible organic and inorganic building blocks, which both resist phase separation and introduce the possibility of synergistic functionality to the material.Here we will demonstrate a novel approach for the preparation of optically-active hybrid supramolecular networks based on the electrostatic co-assembly of cationic CPEs with an anionic lacunary polyoxometalate (POM), K8[SiW10O36]. Using a combination of spectroscopic techniques (UV/Vis absorption, fluorescence, linear dichroism, dynamic light scattering), we observe that the dimensionality of the hybrid network in solution can be tuned from 1D to 2D by changing the molecular weight and steric charge distribution on the CPE. Moreover, atomic force microscopy and scanning electron microscopy studies reveal that the self-assembled hybrid suprastructures generated in solution can be transferred to solid-state thin films. Given the breadth of molecular topologies, surface charge densities, redox and optical properties afforded by both the CPE and POM families, our approach should enable the generation of a variety of well-defined, supramolecular architectures with enhanced functionality.

Design and response of hybrid conjugated polyelectrolyte-polyoxometalate supramolecular networks

248th National Meeting (2014)

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