Herein, we first report a novel approach for preparing 3D π-π stacked crystals of polyaniline and polypyrrole and show how they self-assemble in a suitable solution environment. 3D crystals of polyaniline and polypyrrole show high charge-transport properties of 130 S cm(-1) and 150 S cm(-1), respectively. Remarkably, the 3D crystals of polyaniline obtain excellent anisotropic conductivity.
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