Abstract To investigate the effect of fluorine–hydrogen bonding and metal–ligand coordination on the morphology and gas sensing properties of self-assembled nanostructures, metal free 2,3,9,10,16,17,24,25-octakis(heptafluorobutoxy)phthalocyanine H2[Pc(OCH2C3F7)8] (1) and its zinc complex counterpart Zn[Pc(OCH2C3F7)8] (2) are synthesized and fabricated into organic microstructures by a phase-transfer method. The self-assembling properties have been comparatively investigated by electronic absorption and Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD) and current–voltage (I–V) measurements. Competition and cooperation between the inter-molecular π-π interaction and C-H⋯F-C hydrogen bonding in the direction perpendicular to the π-π interaction direction for metal-free phthalocyanine 1 lead to the formation of uniformed two-dimensional helical microribbons with an aspect ratio (length/width) of ca 20. The additional Zn-O coordination interactions between the central zinc ion and the oxygen atom of the adjacent molecule increases the intermolecular interaction, and results in the formation of long one-dimensional nanowires for 2 with an aspect ratio of more than 200. Notably, the resulting microstructures were revealed to show good semiconducting properties with the increasing conductivity from 5.99 × 10−5 S cm−1 for the nanowires of 2 to 1.68 × 10−4 S cm−1 for the helical ribbons of 1. Moreover, the excellently sensitive, stable and reproducible responses to NO2 in 50–900 ppb range are observed for the helical ribbons of 1 at room temperature, implying the excellent potential as the NO2 sensor for applications in practical environments. Both sensitivity and detection limit of the helical ribbons of 1 for NO2 gas at room temperature was found to be better than those of the nanowires of 2. This suggests that the analyte-phthalocyanine interaction is dominated by not only high conductivity and great surface area but more importantly binding strength of analyte to the central cavity of the phthalocyanine.
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