Effect of ligand congeniality on energy transfer reaction between photo-excited tris(bipyridine)ruthenium(II) and chromate(III) complexes in aqueous solutions |
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| Institution: | 1. School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, PR China;2. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, PR China;1. Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi''an 710069, People''s Republic of China;2. College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People''s Republic of China;3. School of Material Science and Engineering, Beihang University, XueYuan Road No. 37, HaiDian District, Beijing 100191, People''s Republic of China;1. Department of General and Coordination Chemistry, Maria Curie-Sklodowska University, Maria Curie-Sklodowska sq. 2, 20-031 Lublin, Poland;2. Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Kraków, Poland;3. Department of Crystallography, Maria Curie-Sklodowska University, Maria Curie-Sklodowska sq. 3, 20-031 Lublin, Poland;4. Faculty of Chemistry, University of Wroc?aw, F. Joliot Curie 14, 50-383 Wroc?aw, Poland |
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| Abstract: | Energy-transfer rate-constants from photo-excited Ru(N–N)3]2+ (N–N = 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (4dmb), 5,5′-dimethyl-2,2′-bipyridine (5dmb)) to Cr(O–O)3]3? (O–O2? = ox2? ((COO?)2), mal2? (CH2(COO?)2)) and Cr(CN)6]3? in encounter complexes were evaluated in aqueous solutions containing alkali metal ion. The rate constant depends on the molecular size of the ruthenium(II) complex: 1.8 × 108 s?1 for Ru(bpy)3]2+ (molecular radius, r = 5.8 Å), 1.4 × 108 s?1 for Ru(5dmb)3]2+ (r = 6.1 Å) and 0.96 × 108 s?1 for Ru(4dmb)3]2+ (r = 6.7 Å) in the system of Ru(N–N)3]2+–Cr(ox)3]3? in aqueous solution. However, the rate constant is much more sensitive to the chromate(III) complex than to ruthenium(II) complex; 1.8 × 108 s?1 and 0.43 × 108 s?1 for Cr(ox)3]3? (r = 4.0 Å) and Cr(mal)3]3? (r = 4.2 Å) in the Ru(bpy)3]2+–Cr(O–O)3]3? systems, respectively. We conclude that the congeniality between the donor’s and acceptor’s ligands in encounter complex plays an important role in energy transfer in aqueous solution. |
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