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a b s t r a c tA TiO 2 organic sol was synthesised for the preparation of a compact TiO 2 layer on fluorine-doped tin oxide (FTO) glass by a dip-coating technique. The resultant thin film was used for the fabrication of dyesensitized solar cells (DSSCs). The compact layer typically has a thickness of ca. 110 nm as indicated by its SEM, and consists of anatase as confirmed by the XRD pattern. Compared with the traditional DSSCs without this compact layer, the solar energy-to-electricity conversion efficiency, short-circuit current and open-circuit potential of the DSSCs with the compact layer were improved by 33.3%, 20.3%, and 10.2%, respectively. This can be attributed to the merits brought by the compact layer. It can effectively improve adherence of TiO 2 to FTO surface, provide a larger TiO 2 /FTO contact area, and reduce the electron recombination by blocking the direct contact between the redox electrolyte and the conductive FTO surface.Crown

The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrrolidine, piperidine, isoindoline, and azaphenalene) were determined experimentally by cyclic voltammetry in acetonitrile, and also via high-level ab initio molecular orbital calculations. It is shown that the potentials are influenced by the type of ring system, ring substituents and/or groups surrounding the radical moiety. For the pyrrolidine, piperidine, and isoindolines there is excellent agreement (mean absolute deviation of 0.05 V) between the calculated and experimental oxidation potentials; for the azaphenalenes, however, there is an extraordinary discrepancy (mean absolute deviation of 0.60 V), implying that their one-electron oxidation might involve additional processes not considered in the theoretical calculations. This recently developed azaphenalene class of nitroxide represents a new variant of a nitroxide ring fused to an aromatic system and details of the synthesis of five derivatives involving differing aryl substitution are also presented.