Photophysical and Photochemical Studies of Tricarbonyl Rhenium(I) N-Heterocyclic Carbene Complexes Containing Azide and Triazolate Ligands

Rhenium(I) N-heterocyclic carbene (NHC) complexes of the type fac-[Re(CO)3(NHC)L] with either azide or triazolate ancillary ligands L and pyridyl or pyrimidyl substituted imidazolyl units have been prepared and structurally characterised, and their photophysical and photochemical properties studied....

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Main Authors: Simpson, Peter V., Skelton, B., Raiteri, Paolo, Massi, Massimiliano
Format: Journal Article
Published: Royal Society of Chemistry 2016
Online Access:http://purl.org/au-research/grants/arc/FT130100033
http://hdl.handle.net/20.500.11937/17784
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author Simpson, Peter V.
Skelton, B.
Raiteri, Paolo
Massi, Massimiliano
author_facet Simpson, Peter V.
Skelton, B.
Raiteri, Paolo
Massi, Massimiliano
author_sort Simpson, Peter V.
building Curtin Institutional Repository
collection Online Access
description Rhenium(I) N-heterocyclic carbene (NHC) complexes of the type fac-[Re(CO)3(NHC)L] with either azide or triazolate ancillary ligands L and pyridyl or pyrimidyl substituted imidazolyl units have been prepared and structurally characterised, and their photophysical and photochemical properties studied. All of the complexes exhibit phosphorescent emission from triplet metal-to-ligand (3MCLT) excited states, typical of tricarbonyl Re(I) complexes, with the triazolate bound complexes having higher quantum yields and longer decay lifetimes compared to the azide bound complexes. The complexes containing pyridyl substituted imidazolyl units are photoreactive when dissolved in acetonitrile and undergo photochemical CO dissociation, the rate of which is significantly greater in the azide cf. triazolate complex. The photochemical mechanism of the azide/pyridyl complex was analysed and appears to give the same products, albeit with different ratios, to previously reported complexes where L is a halide. A reaction mechanism is proposed.
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spelling curtin-20.500.11937-177842024-04-11T03:19:36Z Photophysical and Photochemical Studies of Tricarbonyl Rhenium(I) N-Heterocyclic Carbene Complexes Containing Azide and Triazolate Ligands Simpson, Peter V. Skelton, B. Raiteri, Paolo Massi, Massimiliano Rhenium(I) N-heterocyclic carbene (NHC) complexes of the type fac-[Re(CO)3(NHC)L] with either azide or triazolate ancillary ligands L and pyridyl or pyrimidyl substituted imidazolyl units have been prepared and structurally characterised, and their photophysical and photochemical properties studied. All of the complexes exhibit phosphorescent emission from triplet metal-to-ligand (3MCLT) excited states, typical of tricarbonyl Re(I) complexes, with the triazolate bound complexes having higher quantum yields and longer decay lifetimes compared to the azide bound complexes. The complexes containing pyridyl substituted imidazolyl units are photoreactive when dissolved in acetonitrile and undergo photochemical CO dissociation, the rate of which is significantly greater in the azide cf. triazolate complex. The photochemical mechanism of the azide/pyridyl complex was analysed and appears to give the same products, albeit with different ratios, to previously reported complexes where L is a halide. A reaction mechanism is proposed. 2016 Journal Article http://hdl.handle.net/20.500.11937/17784 10.1039/C5NJ03301B http://purl.org/au-research/grants/arc/FT130100033 http://purl.org/au-research/grants/arc/FT130100463 http://creativecommons.org/licenses/by-nc/3.0/ Royal Society of Chemistry fulltext
spellingShingle Simpson, Peter V.
Skelton, B.
Raiteri, Paolo
Massi, Massimiliano
Photophysical and Photochemical Studies of Tricarbonyl Rhenium(I) N-Heterocyclic Carbene Complexes Containing Azide and Triazolate Ligands
title Photophysical and Photochemical Studies of Tricarbonyl Rhenium(I) N-Heterocyclic Carbene Complexes Containing Azide and Triazolate Ligands
title_full Photophysical and Photochemical Studies of Tricarbonyl Rhenium(I) N-Heterocyclic Carbene Complexes Containing Azide and Triazolate Ligands
title_fullStr Photophysical and Photochemical Studies of Tricarbonyl Rhenium(I) N-Heterocyclic Carbene Complexes Containing Azide and Triazolate Ligands
title_full_unstemmed Photophysical and Photochemical Studies of Tricarbonyl Rhenium(I) N-Heterocyclic Carbene Complexes Containing Azide and Triazolate Ligands
title_short Photophysical and Photochemical Studies of Tricarbonyl Rhenium(I) N-Heterocyclic Carbene Complexes Containing Azide and Triazolate Ligands
title_sort photophysical and photochemical studies of tricarbonyl rhenium(i) n-heterocyclic carbene complexes containing azide and triazolate ligands
url http://purl.org/au-research/grants/arc/FT130100033
http://purl.org/au-research/grants/arc/FT130100033
http://hdl.handle.net/20.500.11937/17784