Mechanisms and Factors Controlling Photoisomerization Equilibria, Ligand Exchange, and Water Oxidation Catalysis Capabilities of Mononuclear Ruthen­ium(II) Complexes

Abstract

The photoisomerization equilibrium between distal-and proximal- [Ru(tpy)

Visible‐Light‐Induced Morphological Changes of Giant Vesicles by Photoisomerization of a Ruthenium Aqua Complex

“…Scheme1.Irreversible and reversible photoisomerizations of ruthenium aqua complexes. [35,36,39] [a] Dr.…”

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a]Scheme1.Irreversible and reversible photoisomerizations of ruthenium aqua complexes. [35,36,39] [a] Dr.Supporting information and ORCID(s)f rom the author(s) for this articleare available on the WWW under http://dx.

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“…We recently reported irreversible [35][36][37][38] and reversible photoisomerizations [39] of mononuclear ruthenium aqua complexes havinga na symmetric bidentate ligand (Scheme 1). The reversibilityo ft he reactioni sc ontrolled by intramolecular hydrogen bondingb etween the aqua ligand and the pendant moiety of the bidentate ligand.…”

“…We earlier reportedt hat photoisomerization reactions were highly suppressed by deprotonation of the aqua ligand (RuÀOH 2 !RuÀ OH) because the ruthenium hydroxo complex is inactivet owards photoisomerization. [35,36,39] We prepared vesiclesc ontaining proximal-2/DOPC in an aqueous NaOH solution (10 mm), and for comparison, the vesicles were also prepared in 5mm Na 2 SO 4 .I nt he NaOH solution, the MLCT absorption band of the proximal-2/DOPC displayed ar ed-shift of 43 nm from that prepared in water or an aqueous solution of 5mm Na 2 SO 4 . Under basic conditions, only 10 %o fv esicles showed size increases, and neither buddingn or divisiono fv esicles were observed after light irradiation (Supporting Information , Figure S14).…”

Photoisomerization and thermal isomerization of ruthenium aqua complexes with chloro-substituted asymmetric bidentate ligands

“…7 The rst example was cis-trans isomerization of [Ru(2,2 0 -bipyridine) 2 (OH 2 ) 2 ] 2+ , reported by Meyer et al 8 Linkage isomerizations of dimethyl sulfoxide derivatives have been experimentally and mechanistically studied by Rack et al, 4b,9 and were recently used in materials that show lightinduced macroscopic morphological changes. 10 We have reported irreversible 11 and reversible 12 photoisomerizations of mononuclear ruthenium aqua complexes containing asymmetric bidentate ligands. These molecules are important because of their high catalytic activities in water oxidation, which is essential for the development of articial photosynthesis.…”