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Photosensitizing Properties of Alkynylrhenium(I) Complexes [Re(-C≡C-R)­(CO)3(N∩N)] (N∩N = 2,2′-bipy, phen) for H2Production


Oberholzer, Miriam; Probst, Benjamin; Bernasconi, Dominik; Spingler, Bernhard; Alberto, Roger (2014). Photosensitizing Properties of Alkynylrhenium(I) Complexes [Re(-C≡C-R)­(CO)3(N∩N)] (N∩N = 2,2′-bipy, phen) for H2Production. European Journal of Inorganic Chemistry, 2014(19):3002-3009.

Abstract

A series of complexes of the type [fac-Re(X)(CO)(3)(N boolean AND N)] (X = -C C-R, N boolean AND N = 2,2' -bipy, 2,2' -phen) were synthesized and fully characterized. Their photophysical characteristics make them very convenient photosensitizers (PSs). Upon light irradiation, H-2 formation was observed for all alkynyl complexes in the presence of a water-reducing catalyst (WRC) and a sacrificial electron donor. Relative rates of H-2 production indicate a dependency upon the diimine ligands rather than upon the nature of the sigma-bonded alkynyl derivatives. The coordinated acetylene group induces a redshift of the lambda(max) of the MLCT band in UV/Vis spectroscopy as compared to those of the corresponding halides, nitriles, or cationic Re-I complexes, such as [fac-ReX(CO)(3)( N boolean AND N)] (X = pyridine, H2O, N boolean AND N = bipy, phen).

Abstract

A series of complexes of the type [fac-Re(X)(CO)(3)(N boolean AND N)] (X = -C C-R, N boolean AND N = 2,2' -bipy, 2,2' -phen) were synthesized and fully characterized. Their photophysical characteristics make them very convenient photosensitizers (PSs). Upon light irradiation, H-2 formation was observed for all alkynyl complexes in the presence of a water-reducing catalyst (WRC) and a sacrificial electron donor. Relative rates of H-2 production indicate a dependency upon the diimine ligands rather than upon the nature of the sigma-bonded alkynyl derivatives. The coordinated acetylene group induces a redshift of the lambda(max) of the MLCT band in UV/Vis spectroscopy as compared to those of the corresponding halides, nitriles, or cationic Re-I complexes, such as [fac-ReX(CO)(3)( N boolean AND N)] (X = pyridine, H2O, N boolean AND N = bipy, phen).

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:July 2014
Deposited On:24 Oct 2014 17:15
Last Modified:05 Apr 2016 18:26
Publisher:Wiley-Blackwell Publishing, Inc.
ISSN:1434-1948
Publisher DOI:https://doi.org/10.1002/ejic.201402142

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