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Title: Synthesis of new photosensitive H<inf>2</inf>BBQ<sup>2+</sup>[ZnCl<inf>4</inf>]<sup>2−</sup>/[(ZnCl)<inf>2</inf>(μ-BBH)] complexes, through selective oxidation of H<inf>2</inf>O to H<inf>2</inf>O<inf>2</inf>
Authors: Stylianou, Marios 
Hadjiadamou, Ioanna 
Drouza, Chryssoula 
Hayes, Sophia C. 
Lariou, Ε. 
Tantis, Iosif 
Lianos, Panagiotis 
Tsipis, Athanassios C. 
Keramidas A. 
Keywords: Crystallography;Electron spin resonance spectroscopy;Ligands
Category: Agricultural Biotechnology
Field: Agricultural Sciences
Issue Date: 1-Jan-2017
Publisher: Royal Society of Chemistry
Source: Dalton Transactions, 2017, Volume 46, Issue 11, Pages 3688-3699
metadata.dc.doi: 10.1039/c6dt04643f
Abstract: A new two-electron photosensitizer, H2BBQ2+[ZnCl4]2−/[(ZnCl)2(μ-BBH)] (BBQ stands for 2,5-bis[bis(pyridin-2-ylmethyl)amino]-1,4-quinone and BBH stands for 2,5-bis[bis(pyridin-2-ylmethyl)amino]-1,4-hydroquinone), has been synthesized and the oxidation state of the ligand was determined by X-ray crystallography and NMR spectroscopy. Under light illumination the H2BBQ2+[ZnCl4]2− + ZnCl2 is reduced quantitatively to [(ZnCl)2(μ-BBH)] (pH ∼ 5) oxidizing H2O to H2O2 as is evident by trap experiments. Electrochemistry gave a reversible two-electron ligand-centered redox wave for [(ZnCl)2(μ-BBH)]. UV-Vis, luminescence and EPR spectroscopies reveal the slow formation of a stable quinone diradical, intermediate of the reaction. DFT calculations are in agreement with the proposed mechanism. Based on this property an aqueous {[(ZnCl)2(μ-BBH)]||H2O2} solar rechargeable galvanic cell has been constructed.
ISSN: 14779226
Rights: © The Royal Society of Chemistry
Type: Article
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