Four copper(I) complexes have been designed as photosensitizers for assisting the norbornadiene (NBD) --> quadricyclene (Q) isomerization with the purpose of carrying out the reaction using visible light and achieving a high NBD/photocatalyst turnover. All complexes contain pi-delocalized bidentate N asymptotic to O monoanionic ligands. Their syntheses have been performed either by the metathesis reaction from CuCl or by reaction of the monoprotic ligands with Cu(5)Mes(5) (Mes = 2,4,6-Me3C6H2) in the presence of norbornadiene. The dinuclear complexes [Cu2L2(mu-NBD)], 3, [Cu2L'(2)(mu-NBD)], 4, [Cu2L ''(2)(mu-NBD)], 5, and [Cu2L'''(2)(mu-NBD)], 6 [where L = 2-methyl-8-oxoquinolinato, L' = 2-methyl-5,7-dichloro-8-oxoquinolinato, L '' = 4-oxoacridinato, and L''' = 2-(2-oxo-3,5-di-tert-butyl phenyl)benzotriazole], have been isolated and characterized in the solid state, including the X-ray analysis on 3 and 6. All compounds show absorption in the visible spectrum, due to the presence of metal-to-ligand charge-transfer (MLCT) bands. Most were active in assisting the NBD --> Q conversion, although the best results were obtained in the case of 3, for which we give a detailed report. Complex 3 is the precursor, in the presence of NBD, of the photoactive monomeric species [CuL(NBD)], 9, where a single C=C binds copper(I), of which complex 7, [CuL(NBN)] [NBN drop norbornene], can be regarded as a model compound. The NBD photoisomerization assisted by 3 (see 9) has been carried out in methanol by visible light irradiation (lambda = 405 nm) with a photoisomerization quantum yield of 0.029. Turnover numbers (moles of Q produced/mole of photocatalyst) of ca. 5000 were obtained: in this solvent. An increase of the temperature gave rise to a significative quantum yield enhancement. The other compounds were less efficient than 3 in assisting the NBD --> Q photoisomerization under visible light irradiation, most probably due to the low energy of their MLCT excited states.
Designing Copper(I) Photosensitizers for the Norbornadiene-Quadricyclane Transformation Using Visible Light: an Improved Solar Energy Storage System / F., Franceschi; M., Guardigli; E., Solari; C., Floriani; A., Chiesi Villa; Rizzoli, Corrado. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 36:(1997), pp. 4099-4107. [10.1021/ic9706156]
Designing Copper(I) Photosensitizers for the Norbornadiene-Quadricyclane Transformation Using Visible Light: an Improved Solar Energy Storage System
RIZZOLI, Corrado
1997-01-01
Abstract
Four copper(I) complexes have been designed as photosensitizers for assisting the norbornadiene (NBD) --> quadricyclene (Q) isomerization with the purpose of carrying out the reaction using visible light and achieving a high NBD/photocatalyst turnover. All complexes contain pi-delocalized bidentate N asymptotic to O monoanionic ligands. Their syntheses have been performed either by the metathesis reaction from CuCl or by reaction of the monoprotic ligands with Cu(5)Mes(5) (Mes = 2,4,6-Me3C6H2) in the presence of norbornadiene. The dinuclear complexes [Cu2L2(mu-NBD)], 3, [Cu2L'(2)(mu-NBD)], 4, [Cu2L ''(2)(mu-NBD)], 5, and [Cu2L'''(2)(mu-NBD)], 6 [where L = 2-methyl-8-oxoquinolinato, L' = 2-methyl-5,7-dichloro-8-oxoquinolinato, L '' = 4-oxoacridinato, and L''' = 2-(2-oxo-3,5-di-tert-butyl phenyl)benzotriazole], have been isolated and characterized in the solid state, including the X-ray analysis on 3 and 6. All compounds show absorption in the visible spectrum, due to the presence of metal-to-ligand charge-transfer (MLCT) bands. Most were active in assisting the NBD --> Q conversion, although the best results were obtained in the case of 3, for which we give a detailed report. Complex 3 is the precursor, in the presence of NBD, of the photoactive monomeric species [CuL(NBD)], 9, where a single C=C binds copper(I), of which complex 7, [CuL(NBN)] [NBN drop norbornene], can be regarded as a model compound. The NBD photoisomerization assisted by 3 (see 9) has been carried out in methanol by visible light irradiation (lambda = 405 nm) with a photoisomerization quantum yield of 0.029. Turnover numbers (moles of Q produced/mole of photocatalyst) of ca. 5000 were obtained: in this solvent. An increase of the temperature gave rise to a significative quantum yield enhancement. The other compounds were less efficient than 3 in assisting the NBD --> Q photoisomerization under visible light irradiation, most probably due to the low energy of their MLCT excited states.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
