Electrochemical nanopatterning of an electrogenerated photosensitive poly-[trisbipyridinyl-pyrrole ruthenium(II)] metallopolymer by nanosphere lithography

• An electrogenerated Ru(II) metallopolymer was nanostructured using NSL.
• Depending on the size of the nanospheres, highly-organized nanostructures were achieved.
• Photoelectrochemical properties depends on the size of the nanospheres.

900- and 100-nm-diameter polystyrene beads were combined with electrogenerated photosensitive poly-[tris(4,4-bis(3-pyrrol-1-ylpropyloxy)bipyridinyl)ruthenium(II)], (poly-[RuII-pyrrole]), metallopolymer on glassy carbon electrodes. Nanosphere lithography (NSL) with 900-nm-diameter microbead mask affords the realization of a nanostructured polymer (after dissolution of the polystyrene templates) with a typical highly-organized honeycomb nanostructure. NSL with 100-nm-diameter-nanobead mask allowed the achievement of a highly macroporous metallopolymer. The nanostructured Ru(II)-based metallopolymer was characterized by 3D laser scanning confocal microscopy and scanning electron microscopy (SEM). Electrochemical and photoelectrochemical studies demonstrate the enhancement of redox probe diffusion in the polymer layer for nanopatterned poly-[RuII-pyrrole]. This is accompanied with photocurrent enhancement for nanostructured polymer, especially in the case of poly-[RuII-pyrrole] obtained by the 100 nm-nanobead NSL.

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