Ordered Supramolecular Assembly of Porphyrin–Fullerene Composites on Nanostructured SnO2 Electrodes
Source abstract
Abstract
Very high photocurrent generation is seen for an ordered supramolecular composite structure of C60 and porphyrin assembled on SnO2 electrodes. The simple substitution of methoxy groups at the meta positions of the meso-phenyl groups on the porphyrin ring leads to the ordered stacking arrangement shown in the figure, with separate electron and hole transport paths along the 1D porphyrin chains and 2D C60 sheets.
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Research context
OpenAlex topics: Porphyrin and Phthalocyanine Chemistry · Fullerene Chemistry and Applications · Carbon Nanotubes in Composites
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References (39)
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34. The large cubic clusters seen in the SEM image (Fig. 3A) have been determined to be microcrystals by polarized optical microscopy studies. The SEM AFM and optical microscopy results indicate that in the case of the ITO/SnO2/(3 5‐TPP + C60)melectrode some of the initial small clusters in the mixed solvent system form porphyrin–fullerene composite films whereas other clusters grow to form microcrystals which are deposited on the surface of the film. Further growth of the microcrystals leads to the formation of single crystals such as the one used for X‐ray analysis (as discussed below).
35. The action spectrum may result from CT interaction between the porphyrin and C60molecules which is influenced by the relative ratio of the porphyrin and C60molecules as well as by the molecular structure of the porphyrins. Similar action spectra have also been reported for porphyrin–fullerene photoelectrochemical devices [9].
36. The first oxidation potentials due to the porphyrin moiety have been determined to be +1.18 V for 3 5‐TPP +1.16 V for 3 4 5‐TPP and +1.02 V for 2 6‐TPP versus a normal hydrogen electrode (NHE) in dichloromethane containingn‐Bu4NPF6. Thus we can rule out the possibility that differences in the driving forces for photoinduced ET processes affect the IPCE values significantly in the present system.
37. Formula C179H54N4O8 monoclinic space groupP21/c a = 26.214(3) Å b = 16.7238(17) Å c = 26.148(3) Å β = 116.382(4)° V = 10 269.3(19) Å3 Z = 4 Dc = 1.545 g cm–3 19 081 observed Rw = 0.3138 R = 0.1227 (I > 2.00σ(I)) goodness of fit (GOF) = 1.071. Measured at 93 K. CCDC‐289 067 contains the supplementary crystallographic data for this paper. This data can be obtained free of charge from The Cambridge Crystallographic Data Centre (CCDC) atwww.ccdc.cam.ac.uk/data_request/cif. The co‐crystallized solids 3 4 5‐TPP or 2 6‐TPP with C60have not been obtained. The additional bulky methoxy groups at the para positions of themeso‐phenyl groups of 3 4 5‐TPP may disturb the intimate interaction between the porphyrins preventing the formation of a single crystal.
38. Some of the interatomic distances (2.5–2.6 Å) between the hydrogen and oxygen atoms on the methoxy groups of the nearest porphyrins are shorter than the sum of the van der Waals radii of hydrogen and oxygen atoms (2.72 Å) suggesting the involvement of hydrogen bonding in knitting together the unique porphyrin array in the composite film.
39. The small porphyrin to C60ratio (i.e. [H2P]:[C60] = 1:6) results in small clusters being formed initially. Subsequently clusters with the unique molecular arrangement further bind an excess of C60molecules to yield the composite nanoclusters consisting of segregated nanoarrays of porphyrin and C60 with the outside surface covered by C60molecules [9].