Ge complexes of 5,10,15-triphenylcorrole were prepared in refluxing dry DMF using GeCl 4 as the source of Ge. Chromatographic separation of the crude reaction mixture afforded the µ-oxo dimer 1 and the methoxy derivative 2a. The corresponding chloride 2b can be obtained by treatment of 1 or 2a with HCl. The reaction of 2a with Br 2 in CHCl 3 /py afforded the hexabromo derivative 3 as the main product, giving the first indication of the regioselective substitution of pyrroles B and C on the corrole ring. The fully brominated open-chain tetrapyrrole 4 was also characterized as a reac-

Gold nanoparticles functionalized with chromophores are known to present unpredictable fluorescence as a function of their structure. Odd-even effects, based on the number of methylene units of the chain to which the fluorophore is attached, and the nature of the anchoring group on the gold surface have, in the past, been suggested to be responsible for the behavior. Here we investigate the fluorescence processes of two newly synthesized pyrene derivatives bound to gold nanoparticles. Two structurally identical ligands, differing only in the nature of the anchoring group (a thiolate in one case and an amine in the other), were newly synthetized and attached to the gold nanoparticles. The same changes in the fluorescence properties, namely, a red spectral shift with a moderate increase of the quantum yield and a shortening of the excited-state lifetime, are observed in the two cases and ascribed to the proximity of the gold core. By comparison with the results reported for other pyrene derivatives, it has been possible to draw the conclusions that (i) the nature of the binding group does not affect the fluorescence properties of the fluorophores attached to the nanoparticle surface and (ii) much stronger fluorescence is observed in the case of pyrene separated from the gold by short alkyl chain. The unusual behavior is explained in simple terms of competing chain-chain and chromophore-chromophore interactions and by means of proper energy diagrams.

We present here the study of the photophysical properties of new dye-doped silica nanoparticles (DDNs) bearing dansyl fluorescent derivatives covalently linked to the silica matrix. The described experimental evidences show how the different location of the chromophores induces great changes in their photophysical behavior, suggesting that fluorophores located near the surface of the nanoparticles have a very different behavior with respect to the internal molecules. These latter ones, in fact, are shielded from the solvent and have a strong blue emission, while those at the periphery interact with the solvent and show a weaker red-shifted emission. As a consequence, the fluorescence properties of these nanoparticles are an average between the characteristics of the two different families of dyes. The relative amount of fluorophores located in the two compartments can be controlled simply by changing the size since, from our results, the thickness of the solvent permeable layer is not relevantly affected by the diameter of the nanoparticles. It is noteworthy that the fluorophores located in the outer shell exhibit very peculiar features: they are sensitive and interact with small molecules such as solvent molecules but, at the same time, they are not accessible to big receptor species such as beta-cyclodextrins. Such results indicate that most of the solvent-sensitive dansyl moieties are located within pores large enough to only accommodate solvent but not big molecules as cyclodextrins, giving precious insight on the morphology of the nanoparticles.

We report here the monitoring of reversible guest inclusion in phosphonate cavitands through a large increase in luminescence intensity caused by the modulation of the exoergonicity of an electron-transfer reaction.