Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes
<p dir="ltr">A series of [Re(N^N)(CO)<sub>3</sub>(Cl)] (N^N = diimine) complexes based on 4-(pyrid-2-yl)-1,2,3-triazole (1), 1-benzyl-4-(pyrimidin-2-yl)-1,2,3-triazole (2), and 1-benzyl-4-(pyrazin-2-yl)-1,2,3-triazole (3) diimine ligands were prepared and their photophysi...
محفوظ في:
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| مؤلفون آخرون: | , , , , |
| منشور في: |
2020
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| _version_ | 1864513505272528896 |
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| author | Adrian Comia (8298180) |
| author2 | Luke Charalambou (8298177) Salem A. E. Omar (5860493) Paul A. Scattergood (1922995) Paul I. P. Elliott (8298183) Alessandro Sinopoli (4318555) |
| author2_role | author author author author author |
| author_facet | Adrian Comia (8298180) Luke Charalambou (8298177) Salem A. E. Omar (5860493) Paul A. Scattergood (1922995) Paul I. P. Elliott (8298183) Alessandro Sinopoli (4318555) |
| author_role | author |
| dc.creator.none.fl_str_mv | Adrian Comia (8298180) Luke Charalambou (8298177) Salem A. E. Omar (5860493) Paul A. Scattergood (1922995) Paul I. P. Elliott (8298183) Alessandro Sinopoli (4318555) |
| dc.date.none.fl_str_mv | 2020-03-24T09:00:00Z |
| dc.identifier.none.fl_str_mv | 10.3390/inorganics8030022 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/journal_contribution/Photophysical_and_Electrocatalytic_Properties_of_Rhenium_I_Triazole-Based_Complexes/27021574 |
| dc.rights.none.fl_str_mv | CC BY 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Chemical sciences Inorganic chemistry Physical chemistry rhenium complexes triazole ligands luminescence electrocatalysis |
| dc.title.none.fl_str_mv | Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes |
| dc.type.none.fl_str_mv | Text Journal contribution info:eu-repo/semantics/publishedVersion text contribution to journal |
| description | <p dir="ltr">A series of [Re(N^N)(CO)<sub>3</sub>(Cl)] (N^N = diimine) complexes based on 4-(pyrid-2-yl)-1,2,3-triazole (1), 1-benzyl-4-(pyrimidin-2-yl)-1,2,3-triazole (2), and 1-benzyl-4-(pyrazin-2-yl)-1,2,3-triazole (3) diimine ligands were prepared and their photophysical and electrochemical properties were characterized. The ligand-based reduction wave is shown to be highly sensitive to the nature of the triazole-based ligand, with the peak potential shifting by up to 600 mV toward more positive potential from 1 to 3. All three complexes are phosphorescent in solution at room temperature with λmax ranging from 540 nm (1) to 638 nm (3). Interestingly, the complexes appear to show inverted energy-gap law behaviour (τ = 43 ns for 1 versus 92 ns for 3), which is tentatively interpreted as reduced thermal accessibility of metal-centred (<sup>3</sup>MC) states from photoexcited metal to ligand charge transfer (<sup>3</sup>MLCT) states upon stabilisation of the N^N-centred lowest unoccupied molecular orbital (LUMO). The photophysical characterisation, supported by computational data, demonstrated a progressive stabilization of the LUMO from complex 1 to 3, which results in a narrowing of the HOMO–LUMO energy gap (HOMO = highest occupied molecular orbital) across the series and, correspondingly, red-shifted electronic absorption and photoluminescence spectra. The two complexes bearing pyridyl (1) and pyrimidyl (2) moieties, respectively, showed a modest ability to catalyse the electroreduction of CO<sub>2</sub>, with a peak potential at ca. −2.3 V versus Fc/Fc+. The catalytic wave that is observed in the cyclic voltammograms is slightly enhanced by the addition of water as a proton source.</p><h2>Other Information</h2><p dir="ltr">Published in: Inorganics<br>License: <a href="https://creativecommons.org/licenses/by/4.0/" target="_blank">https://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.3390/inorganics8030022" target="_blank">https://dx.doi.org/10.3390/inorganics8030022</a></p> |
| eu_rights_str_mv | openAccess |
| id | Manara2_4f50732682cc129647e606d063980a87 |
| identifier_str_mv | 10.3390/inorganics8030022 |
| network_acronym_str | Manara2 |
| network_name_str | Manara2 |
| oai_identifier_str | oai:figshare.com:article/27021574 |
| publishDate | 2020 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY 4.0 |
| spelling | Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based ComplexesAdrian Comia (8298180)Luke Charalambou (8298177)Salem A. E. Omar (5860493)Paul A. Scattergood (1922995)Paul I. P. Elliott (8298183)Alessandro Sinopoli (4318555)Chemical sciencesInorganic chemistryPhysical chemistryrheniumcomplexestriazoleligandsluminescenceelectrocatalysis<p dir="ltr">A series of [Re(N^N)(CO)<sub>3</sub>(Cl)] (N^N = diimine) complexes based on 4-(pyrid-2-yl)-1,2,3-triazole (1), 1-benzyl-4-(pyrimidin-2-yl)-1,2,3-triazole (2), and 1-benzyl-4-(pyrazin-2-yl)-1,2,3-triazole (3) diimine ligands were prepared and their photophysical and electrochemical properties were characterized. The ligand-based reduction wave is shown to be highly sensitive to the nature of the triazole-based ligand, with the peak potential shifting by up to 600 mV toward more positive potential from 1 to 3. All three complexes are phosphorescent in solution at room temperature with λmax ranging from 540 nm (1) to 638 nm (3). Interestingly, the complexes appear to show inverted energy-gap law behaviour (τ = 43 ns for 1 versus 92 ns for 3), which is tentatively interpreted as reduced thermal accessibility of metal-centred (<sup>3</sup>MC) states from photoexcited metal to ligand charge transfer (<sup>3</sup>MLCT) states upon stabilisation of the N^N-centred lowest unoccupied molecular orbital (LUMO). The photophysical characterisation, supported by computational data, demonstrated a progressive stabilization of the LUMO from complex 1 to 3, which results in a narrowing of the HOMO–LUMO energy gap (HOMO = highest occupied molecular orbital) across the series and, correspondingly, red-shifted electronic absorption and photoluminescence spectra. The two complexes bearing pyridyl (1) and pyrimidyl (2) moieties, respectively, showed a modest ability to catalyse the electroreduction of CO<sub>2</sub>, with a peak potential at ca. −2.3 V versus Fc/Fc+. The catalytic wave that is observed in the cyclic voltammograms is slightly enhanced by the addition of water as a proton source.</p><h2>Other Information</h2><p dir="ltr">Published in: Inorganics<br>License: <a href="https://creativecommons.org/licenses/by/4.0/" target="_blank">https://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.3390/inorganics8030022" target="_blank">https://dx.doi.org/10.3390/inorganics8030022</a></p>2020-03-24T09:00:00ZTextJournal contributioninfo:eu-repo/semantics/publishedVersiontextcontribution to journal10.3390/inorganics8030022https://figshare.com/articles/journal_contribution/Photophysical_and_Electrocatalytic_Properties_of_Rhenium_I_Triazole-Based_Complexes/27021574CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/270215742020-03-24T09:00:00Z |
| spellingShingle | Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes Adrian Comia (8298180) Chemical sciences Inorganic chemistry Physical chemistry rhenium complexes triazole ligands luminescence electrocatalysis |
| status_str | publishedVersion |
| title | Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes |
| title_full | Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes |
| title_fullStr | Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes |
| title_full_unstemmed | Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes |
| title_short | Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes |
| title_sort | Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes |
| topic | Chemical sciences Inorganic chemistry Physical chemistry rhenium complexes triazole ligands luminescence electrocatalysis |