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

作者：Word Tarah A; Karolak Aleksandra; Cioce Christian R; Van Der Vaart Arjan; Larsen Randy W^*

来源：Comments on Inorganic Chemistry, 2016, 36(6): 343-354.

DOI：10.1080/02603594.2016.1183488

• Ru(II)bipyridine
• photoacoustic calorimetry
• ligand photorelease
• ligand photoexchange
• cis-trans isomerization

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 Delta H of -27 +/- 5 kcal mol(-1) and Delta V of 0.1 +/- 2 mL mol(-1). The DFT calculations give a Delta Ecis-trans of + 12 kcal mol-1, indicating that the observed Delta H 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.

• 出版日期2016