Organic Nanostructures with Controllable Morphology Fabricated from Ferrocene–Porphyrin Derivatives: Effect of Metal–Ligand Coordination on the Morphology, Dimensions, and Semiconductor Properties of Self‐Assembled Nanostructures

Two new ferrocene–porphyrin derivatives, namely 5,15‐bis(ferrocenyl)‐10,20‐bis(4‐nitrophenyl)porphyrin ( 1 ) and its nickel congener 5,15‐bis(ferrocenyl)‐10,20‐bis(4‐nitrophenyl)porphyrinatonickel ( 2 ) have been designed, synthesized, and characterized. Their self‐assembly properties have been comparatively studied by electronic absorption and FTIR spectroscopy, TEM, SEM, XRD, and X‐ray photoelectron spectroscopy (XPS). Metal‐free 1 self‐assembles into nanospheres with diameters in the range of 30–50 nm, depending mainly on intermolecular π–π interactions. In contrast, the coordination of nickel to 1 introduces an additional Ni–O coordination bond between the nitryl group of one molecule of 2 and the nickel center of the neighboring 2 unit, which, in cooperation with the intermolecular π–π interaction, induces the formation of nanobelts (ca. 50–300 μm length, 10–50 nm width) during the self‐assembly process of 2 .