Bibliographic Details
| Title: |
Using Photoacoustic Calorimetry to Study the cis- to trans- Photoisomerization of the [Ru(II)(2,2’-bipyridine)2(H2O)2]2+ Complex in Aqueous Solution. |
| Authors: |
Word, Tarah A.1 (AUTHOR), Karolak, Aleksandra2 (AUTHOR), Cioce, Christian R.3 (AUTHOR), Van Der Vaart, Arjan4 (AUTHOR), Larsen, Randy W.4 (AUTHOR) rwlarsen@usf.edu |
| Source: |
Comments on Inorganic Chemistry. 2016, Vol. 36 Issue 6, p343-354. 12p. 1 Color Photograph, 1 Diagram, 2 Charts, 3 Graphs. |
| Subject Terms: |
*CALORIMETRY, *PHOTOISOMERIZATION, *RUTHENIUM compounds, *PHOTOACOUSTIC effect, *DENSITY functional theory, *ISOMERIZATION, *PHOTOLYSIS (Chemistry) |
| Abstract: |
The mechanism associated with the cis- to trans-photoisomerization of Ru(II)(2,2’-bipyridine)2(H2O)2 ([Ru(bpy)2(H2O)2]2+) complex in water has been examined using photoacoustic calorimetry (PAC) and density functional theory (DFT). Photolysis of the cis-[Ru(bpy)2(H2O)2]2+ complex results in a ΔH of -27 ±5 kcal mol–1 and ΔV of 0.1±2 mL mol–1. The DFT calculations give a ΔEcis-trans of +12 kcal mol–1, indicating that the observed ΔH contains significant contributions from changes in solvation. The DFT analysis of putative intermediates [Ru(bpy)2(H2O)]2+ and [Ru(bpy)2(H2O)3]2+ suggests the possibility of an associative mechanism for the isomerization process. [ABSTRACT FROM AUTHOR] |
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