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Hybridization of layered niobates with cationic dyes

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The hybridization of two different types of organic polycations, 1,1′-dimethyl-4,4′-bipyridinium dications (methyl viologen, MV2+) and 5,10,15,20-tetrakis(N-methyl-pyridinium-4-yl)21H,23H-porphine tetracations (TMPyP4+), into layered niobates was investigated to construct an efficient dye-modified semiconductor for solar conversion and storage. Two different methods were employed for the direct intercalation of the cationic species, i.e., conventional ion-exchange with K4Nb6O17 · 3H2O as the starting host and a novel acid–base neutralization method with H4Nb6O17 as the starting host. These two methods showed totally different behavior and the characteristic features of both will be discussed in relation to the structure of the hybrid formed, the amount of absorption observed for the guest molecules and the intercalation rates. An analysis of the photo-induced electron-transfer reactions will also be discussed to show how control of the intercalation of guest molecules affects the photofunctionality of these unique hybrids.


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