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|Type:||Artigo de periódico|
|Title:||Contrasting Photoelectrochemical Behaviour Of Two Isomeric Supramolecular Dyes Based On Meso-tetra(pyridyl)porphyrin Incorporating Four (μ3-oxo)- Triruthenium(iii) Clusters|
|Abstract:||A saddle shaped tetracluster porphyrin species containing four [Ru 3O(OAc)6(py)2]+ clusters coordinated to the N-pyridyl atoms of 5,10,15,20-tetra(3-pyridyl)porphyrin, H 2(3-TCPyP), has been investigated in comparison with the planar tetra(4-pyridyl)porphyrin analogue H2(4-TCPyP). The steric effects from the bulky peripheral complexes play a critical role in the H 2(3-TCPyP) species, determining a non-planar configuration around the porphyrin centre and precluding any significant π-electronic coupling, in contrast with the less hindered H2(4-TCPyP) species. Both systems exhibit a photoelectrochemical response in the presence of nanocrystalline TiO2 films, involving the porphyrin excitation around 450 nm. However, only in the H2(4-TCPyP) case do the cluster moieties also contribute to the photoinduced electron injection process at 670 nm, reflecting the relevance of the electronic coupling between the porphyrin centre and the peripheral complexes. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.|
|Appears in Collections:||Unicamp - Artigos e Outros Documentos|
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