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Title: Cis-trans photoisomerization in Ru(bpy)/sub 2/(OH/sub 2/)/sub 2//sup 2 +/. Crystal structure of trans-(Ru(bpy)/sub 2/(OH/sub 2/)(OH))(ClO/sub 4/)/sub 2/

Abstract

The cis reversible trans photoisomerization of Ru(bpy)/sub 2/(OH/sub 2/)/sub 2//sup 2 +/ in acidic aqueous solution has been investigated. The reaction is independent of the wavelength of irradiation and occurs with quantum yields of 0.043 (cis ..-->.. trans) and 0.025 (trans ..-->.. cis). In the presence of ClO/sub 4//sup -/ the photochemical oxidation of Ru(bpy)/sub 2/(OH/sub 2/)/sub 2//sup 2 +/ to Ru(bpy)/sub 2/(OH/sub 2/)(OH)/sup 2 +/ occurs and the quantum efficiency for this reaction is linearly dependent on (ClO/sub 4//sup -/). The isomerization and oxidation reactions are interpreted as occurring by a dissociative pathway which results from the thermal population of a low lying d-d state which lies above a lowest lying metal-ligand charge-transfer state. The crystal structure of trans-(Ru(bpy)/sub 2/(OH/sub 2/)OH)(ClO/sub 4/)/sub 2/ has been determined from three-dimensional x-ray counter data. The complex crystallizes in the trigonal space group P3/sub 1/21 with three formula units in a cell of dimensions a = 10.902 (2), c = 17.070 (40 A. The structure has been refined to a final value of the conventional R factor of 0.031 based on 2259 independent observations. The geometry of the complex is roughly octahedral, with Ru-N bonds of 2.090 (3) and 2.099 (3) A. Themore » Ru atom lies on a twofold axis, which constrains the two coordinated oxygen atoms to be equivalent; the additional hydrogen atom formally associated with the water ligand forms a symmetrical hydrogen bond to the hydroxyl ligand on an adjacent ion. The Ru-O distance is 2.007 (3) A.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Univ. of North Carolina, Chapel Hill
OSTI Identifier:
5313034
DOE Contract Number:  
ER-78-S-05-6034
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 102:2
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BIPYRIDINES; CRYSTAL STRUCTURE; OXIDATION; PHOTOCHEMISTRY; CHLORATES; RUTHENIUM COMPLEXES; EXPERIMENTAL DATA; ISOLATED VALUES; ISOMERIZATION; AZINES; CHEMICAL REACTIONS; CHEMISTRY; CHLORINE COMPOUNDS; COMPLEXES; DATA; DATA FORMS; HALOGEN COMPOUNDS; HETEROCYCLIC COMPOUNDS; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; OXYGEN COMPOUNDS; PYRIDINES; TRANSITION ELEMENT COMPLEXES; 400500* - Photochemistry

Citation Formats

Durham, B, Wilson, S R, Hodgson, D J, and Meyer, T J. Cis-trans photoisomerization in Ru(bpy)/sub 2/(OH/sub 2/)/sub 2//sup 2 +/. Crystal structure of trans-(Ru(bpy)/sub 2/(OH/sub 2/)(OH))(ClO/sub 4/)/sub 2/. United States: N. p., 1980. Web. doi:10.1021/ja00522a026.
Durham, B, Wilson, S R, Hodgson, D J, & Meyer, T J. Cis-trans photoisomerization in Ru(bpy)/sub 2/(OH/sub 2/)/sub 2//sup 2 +/. Crystal structure of trans-(Ru(bpy)/sub 2/(OH/sub 2/)(OH))(ClO/sub 4/)/sub 2/. United States. https://doi.org/10.1021/ja00522a026
Durham, B, Wilson, S R, Hodgson, D J, and Meyer, T J. Wed . "Cis-trans photoisomerization in Ru(bpy)/sub 2/(OH/sub 2/)/sub 2//sup 2 +/. Crystal structure of trans-(Ru(bpy)/sub 2/(OH/sub 2/)(OH))(ClO/sub 4/)/sub 2/". United States. https://doi.org/10.1021/ja00522a026.
@article{osti_5313034,
title = {Cis-trans photoisomerization in Ru(bpy)/sub 2/(OH/sub 2/)/sub 2//sup 2 +/. Crystal structure of trans-(Ru(bpy)/sub 2/(OH/sub 2/)(OH))(ClO/sub 4/)/sub 2/},
author = {Durham, B and Wilson, S R and Hodgson, D J and Meyer, T J},
abstractNote = {The cis reversible trans photoisomerization of Ru(bpy)/sub 2/(OH/sub 2/)/sub 2//sup 2 +/ in acidic aqueous solution has been investigated. The reaction is independent of the wavelength of irradiation and occurs with quantum yields of 0.043 (cis ..-->.. trans) and 0.025 (trans ..-->.. cis). In the presence of ClO/sub 4//sup -/ the photochemical oxidation of Ru(bpy)/sub 2/(OH/sub 2/)/sub 2//sup 2 +/ to Ru(bpy)/sub 2/(OH/sub 2/)(OH)/sup 2 +/ occurs and the quantum efficiency for this reaction is linearly dependent on (ClO/sub 4//sup -/). The isomerization and oxidation reactions are interpreted as occurring by a dissociative pathway which results from the thermal population of a low lying d-d state which lies above a lowest lying metal-ligand charge-transfer state. The crystal structure of trans-(Ru(bpy)/sub 2/(OH/sub 2/)OH)(ClO/sub 4/)/sub 2/ has been determined from three-dimensional x-ray counter data. The complex crystallizes in the trigonal space group P3/sub 1/21 with three formula units in a cell of dimensions a = 10.902 (2), c = 17.070 (40 A. The structure has been refined to a final value of the conventional R factor of 0.031 based on 2259 independent observations. The geometry of the complex is roughly octahedral, with Ru-N bonds of 2.090 (3) and 2.099 (3) A. The Ru atom lies on a twofold axis, which constrains the two coordinated oxygen atoms to be equivalent; the additional hydrogen atom formally associated with the water ligand forms a symmetrical hydrogen bond to the hydroxyl ligand on an adjacent ion. The Ru-O distance is 2.007 (3) A.},
doi = {10.1021/ja00522a026},
url = {https://www.osti.gov/biblio/5313034}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 102:2,
place = {United States},
year = {1980},
month = {1}
}