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Ligand-selective photodissociation from [Ru(bpy)(4AP)(4)](2+) : a spectroscopic and computational study
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Salassa, Luca, Garino, Claudio, Salassa, Giovanni, Nervi, Carlo, Gobetto, Roberto, Lamberti, Carlo, Gianolio, Diego, Bizzarri, Ranieri and Sadler, P. J. (2009) Ligand-selective photodissociation from [Ru(bpy)(4AP)(4)](2+) : a spectroscopic and computational study. Inorganic Chemistry, Vol.48 (No.4). pp. 1469-1481. doi:10.1021/ic8015436 ISSN 0020-1669.
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Official URL: http://dx.doi.org/10.1021/ic8015436
Abstract
The new complex [Ru(bpy)(4AP)(4))2(+) (1), where bpy = 2,2'-bipyridine and 4AP = 4-aminopyridine, undergoes selective photodissociation of two 4APs upon light excitation of the metal-ligand-to-ligand charge-transfer (MLLCT) band at 510 nm. The photoproducts of the reaction are mer-[Ru(bpy)(4AP)(3)(H2O)](2+) (2a) and trans(4AP)[Ru(bpy)(4AP)(2)(H2O)(2)](2+) (3a). Photodissociation occurs in two consecutive steps with quantum yields of phi(1) = (6.1 +/- 1.0) x 10(-3) and phi(2) = (1.7 +/- 0.1) x 10(-4), respectively. Complex 1 was characterized by combined spectroscopic and theoretical techniques. EXAFS experiments at the Ru K-edge (22 117 eV) of 1 in an aqueous solution gave a Ru-N distance of 2.09 +/- 0.01 angstrom. Photoproducts were characterized by electronic spectroscopy, 1D and 2D NMR, and mass spectrometry. Singlet and triplet excited states of 1 were studied by density functional theory (DFT) and time-dependent DFT for characterizing the optical properties of the complex. In the singlet state, (MC)-M-1 (metal-centered) dissociative states lie 0.65 eV above the main (MLLCT)-M-1 transition in the visible region of the UV-vis absorption spectrum. In the triplet state, the energy difference between these states is not reduced. However, potential energy curves of singlet and triplet excited states of 1 along the Ru-N(axial 4AP) and Ru-N(equatorial 4AP) stretching coordinates show that the release of the first 4AP may occur from the triplet state by mixing of (MLLCT)-M-3 and (MC)-M-3 dissociative states. This mixing is favored when the Ru-N(equatorial 4AP) bond is elongated, explaining the formation of the photoproduct 2a.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QC Physics Q Science > QD Chemistry |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Photodissociation, Metal complexes, Spectrum analysis, Density functionals | ||||
Journal or Publication Title: | Inorganic Chemistry | ||||
Publisher: | American Chemical Society | ||||
ISSN: | 0020-1669 | ||||
Official Date: | 16 February 2009 | ||||
Dates: |
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Volume: | Vol.48 | ||||
Number: | No.4 | ||||
Number of Pages: | 13 | ||||
Page Range: | pp. 1469-1481 | ||||
DOI: | 10.1021/ic8015436 | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access | ||||
Funder: | Seventh Framework Programme (European Commission) (FP7) | ||||
Grant number: | IEF 220281 PHOTORUACD (FP7) |
Data sourced from Thomson Reuters' Web of Knowledge
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