New Multi-Ferrocenyl- and Multi-Ferricenyl- Materials via Coordination-Driven Self-Assembly and via Charge-Driven Electro-Crystallization

Three
new tetra-ferrocenylethynylpyridinyl copper complexes, L4(CuI)4 (3), L4(CuBr)2 (4), and L4(CuCl)2 (5) have been prepared from the reaction of ferrocenyl­ethynyl­pyridine
(L)­(2) with copper halides CuX (with X = I–, Br–, Cl–).The ligand 2 and the complexes 3–5 have
been fully characterized by spectroscopic methods. The structures
of 2–4 have been confirmed by single-crystal
X-ray crystallography. 2 forms a dimer in the crystalline-state
through C–H··N hydrogen bonds. 4 and 5 are dimers and 3 a tetramer, in all cases linked
through Cu–X··Cu bridging interactions. Cyclic voltammetry
in dichloroethane showed chemically reversible multiferrocenyl oxidation
signals with evidence for product electro-crystallization. The oxidation
products were isolated by electrodeposition onto a Pt disc electrode
and investigated by scanning electron microscopy which confirmed the
spontaneous formation of crystalline oxidation products with distinctive
morphologies. Energy dispersive X-ray elemental analysis shows the
presence of hexafluorophosphate (counterion) with the P:Fe ratio of
1:1, 0.5:1, and 1:1 for the electrocrystallized products 3, 4, and 5, respectively, suggesting the
formulas [3]4+(PF6–)4, [4]2+(PF6–)2, and [5]4+(PF6–)4 for the electro-crystallized products.