The covalent and noncovalent interactions of porphyrins and related tetraazamacrocyclic compounds with single-walled carbon nanotubes (SWNTs) is a subject of increasing research effort, directed toward the design of novel hybrid nanomaterials combining unique electronic and optical properties of both molecular species. In this report, we used different experimental techniques as well as molecular mechanics (MM) calculations to analyze the adsorption of meso-tetraphenylporphine (or 5,10,15,20-tetraphenyl-21H,23H-porphine, H2TPP) and its complexes with Ni(II) and Co(II) (NiTPP and CoTPP, respectively), as well as hemin (a natural porphyrin), onto the surface of SWNTs. Altogether, the results suggested that all four porphyrin species noncovalently interact with SWNTs, forming hybrid nanomaterials. Nevertheless, of all four porphyrin species, the strongest interaction with SWNTs occurs in the case of CoTPP, which is able to intercalate and considerably disperse SWNT bundles, and therefore absorb onto the surface of individual SWNTs. In contrast, NiTPP, CoTPP and hemin, due to a weaker interaction, are unable to do so and therefore are only capable to adsorb onto the surface of SWNT bundles. According to the scanning tunneling microscopy (STM) imaging and MM results, the adsorption of CoTPP onto SWNT sidewalls results in the formation of porphyrin arrays in the shape of long-period interacting helixes with variable periodicity, possibly due to different diameters and chiralities of SWNTs present in the samples. Since the remaining porphyrin species were found to adsorb onto the surface of SWNT bundles, the precise geometry of the corresponding porphyrin/SWNT complexes is difficult to characterize. (c) 2013 Elsevier B.V. All rights reserved.