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2O (0.25 mmol) in 5 mL of distilled water. In most cases, the immediate formation of a precipitate was observed. The yellow mixture was stirred for 2 h and then filtered. The yellow precipitate was washed with small amounts of ethanol and diethyl ether. In order to increase the yields, the filtrate solution was further concentrated.
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2O (0.25 mmol) in 5 mL of distilled water. In most cases, the immediate formation of a precipitate was observed. The yellow mixture was stirred for 2 h and then filtered. The yellow precipitate was washed with small amounts of ethanol and diethyl ether. In order to increase the yields, the filtrate solution was further concentrated.
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Electrochemical measurements were carried out at ambient temperature in a 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6, Fluka electrochemical grade)/acetonitrile (Sigma Aldrich, HPLC grade) solution with an analyte concentration of 2 mM. The solvent was dried over 8-12 mesh molecular sieves (Aldrich, and the analyte solution was purged with argon and kept under argon atmosphere during measurement. A conventional three-electrode system connected to a CH Instruments electrochemical workstation (CHI660C) was used. The reference electrode (Ag/AgCl in saturated KClaq) that was kept in a separate compartment filled with electrolyte solution and connected to the analyte solution by a glass frit was calibrated versus ferrocene using the same conditions as for the sample after each measurement series. A commercial glassy carbon electrode with a diameter of 3 mm was used as working electrode, and a freshly annealed platinum wire served as auxiliary electrode. The
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aq) that was kept in a separate compartment filled with electrolyte solution and connected to the analyte solution by a glass frit was calibrated versus ferrocene using the same conditions as for the sample after each measurement series. A commercial glassy carbon electrode with a diameter of 3 mm was used as working electrode, and a freshly annealed platinum wire served as auxiliary electrode. The glassy carbon working electrode was polished on 0.3 alumina (Buehler) before each series of measurement or, when required due to adsorption of the analyte, after each measurement. Cyclic voltammograms (CV) were typically recorded at a scan rate of 0.1 V/s, and the reported data are from reproducible voltammograms from multiple consecutive scans centered on the recorded redox process.
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Following a modified procedure of Reedijk and co-workers,22,23 for the synthesis of the BIAP complexes, we added a solution of the BIAP ligand (0.5 mmol) in 1 mL of methanol to a solution of Mn(ClO4) 2·6H2O (0.5 mmol) in 1 mL of methanol. After 10 min of stirring under nitrogen, a solution of the corresponding benzoic acid derivative (1.0 mmol in 1 mL of H2O, X, H, sodium salt; 1.0 mmol in 1 mL of CH3CN, addition of 10 drops of triethylamine, X, Cl, OCH3, CH3 NO2) was added. In most cases, the formation of a white precipitate was observed. Usually, about 10 mL of H 2O was added in order to increase the yield. The precipitate was filtered off and washed with small amounts of water and dried
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2O was added in order to increase the yield. The precipitate was filtered off and washed with small amounts of water and dried.
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