Acetylenic Substituent: Influence on the Structure, Electrochemical, Photophysical, and Thermal Properties of Rhenium(I) and Platinum(II) Complexes
The ‘wire-like’ acetylenic moiety is an important building block in organic and coordination chemistry that can facilitate electron transfer in donor–acceptor compounds, contributing to the enhancement of their photophysical properties. 2,6-Bis-(thiazol-2-yl)pyridine (<i>dtpy</i>) functi...
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| author | Bartosz Zowiślok Anna Świtlicka Anna Maria Maroń Sławomir Kula |
| author_facet | Bartosz Zowiślok Anna Świtlicka Anna Maria Maroń Sławomir Kula |
| author_sort | Bartosz Zowiślok |
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| description | The ‘wire-like’ acetylenic moiety is an important building block in organic and coordination chemistry that can facilitate electron transfer in donor–acceptor compounds, contributing to the enhancement of their photophysical properties. 2,6-Bis-(thiazol-2-yl)pyridine (<i>dtpy</i>) functionalized with a 4-phenylacetylene group (Ph-C≡C-<i>dtpy</i>) was, for the first time, used for the preparation of [ReCl(CO)<sub>3</sub>(Ph-C≡C-<i>dtpy</i>)] and [Pt(Ph-C≡C-<i>dtpy</i>)Cl]CF<sub>3</sub>SO<sub>3</sub> in order to understand the properties derived from the use of the acetylenic substituent. The coordination ability of Ph-C≡C-<i>dtpy</i> toward Pt(II) and Re(I) centers was determined. All the studied compounds were characterized using FT-IR, <sup>1</sup>H NMR, and <sup>13</sup>C NMR spectroscopies, elemental analysis and, in the case of the free ligand and rhenium(I) complex, single-crystal X-ray analysis was also used. Their electrochemical, photophysical, and thermal properties were compared with the previously described similar systems. The photoluminescence spectra of Ph-C≡C-<i>dtpy</i>, [ReCl(CO)<sub>3</sub>(Ph-C≡C-<i>dtpy</i>)] and [Pt(Ph-C≡C-<i>dtpy</i>)Cl]CF<sub>3</sub>SO<sub>3</sub> were investigated in solution and in the solid state at 298 K and 77 K. The experimental results were supported by the DFT and TD-DFT calculations. As a result of the introduction of the -C≡C- moiety into the organic ligand skeleton, the Re(I) and Pt(II) complexes display room-temperature emission. In the case of [Pt(Ph-C≡C-<i>dtpy</i>)Cl]CF<sub>3</sub>SO<sub>3</sub>, photoluminescence lifetime in a microsecond regime was observed, whereas nanosecond lifetime for [ReCl(CO)<sub>3</sub>(Ph-C≡C-<i>dtpy</i>)] in solution is comparable to lifetimes previously observed for rhenium(I) compounds with 4-substituted <i>dtpys</i>. |
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| spelling | doaj-art-559f32efa1be412286d4140ece4885d32025-08-20T02:03:32ZengMDPI AGMolecules1420-30492025-02-0130491510.3390/molecules30040915Acetylenic Substituent: Influence on the Structure, Electrochemical, Photophysical, and Thermal Properties of Rhenium(I) and Platinum(II) ComplexesBartosz Zowiślok0Anna Świtlicka1Anna Maria Maroń2Sławomir Kula3Institute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice, PolandInstitute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice, PolandInstitute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice, PolandInstitute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice, PolandThe ‘wire-like’ acetylenic moiety is an important building block in organic and coordination chemistry that can facilitate electron transfer in donor–acceptor compounds, contributing to the enhancement of their photophysical properties. 2,6-Bis-(thiazol-2-yl)pyridine (<i>dtpy</i>) functionalized with a 4-phenylacetylene group (Ph-C≡C-<i>dtpy</i>) was, for the first time, used for the preparation of [ReCl(CO)<sub>3</sub>(Ph-C≡C-<i>dtpy</i>)] and [Pt(Ph-C≡C-<i>dtpy</i>)Cl]CF<sub>3</sub>SO<sub>3</sub> in order to understand the properties derived from the use of the acetylenic substituent. The coordination ability of Ph-C≡C-<i>dtpy</i> toward Pt(II) and Re(I) centers was determined. All the studied compounds were characterized using FT-IR, <sup>1</sup>H NMR, and <sup>13</sup>C NMR spectroscopies, elemental analysis and, in the case of the free ligand and rhenium(I) complex, single-crystal X-ray analysis was also used. Their electrochemical, photophysical, and thermal properties were compared with the previously described similar systems. The photoluminescence spectra of Ph-C≡C-<i>dtpy</i>, [ReCl(CO)<sub>3</sub>(Ph-C≡C-<i>dtpy</i>)] and [Pt(Ph-C≡C-<i>dtpy</i>)Cl]CF<sub>3</sub>SO<sub>3</sub> were investigated in solution and in the solid state at 298 K and 77 K. The experimental results were supported by the DFT and TD-DFT calculations. As a result of the introduction of the -C≡C- moiety into the organic ligand skeleton, the Re(I) and Pt(II) complexes display room-temperature emission. In the case of [Pt(Ph-C≡C-<i>dtpy</i>)Cl]CF<sub>3</sub>SO<sub>3</sub>, photoluminescence lifetime in a microsecond regime was observed, whereas nanosecond lifetime for [ReCl(CO)<sub>3</sub>(Ph-C≡C-<i>dtpy</i>)] in solution is comparable to lifetimes previously observed for rhenium(I) compounds with 4-substituted <i>dtpys</i>.https://www.mdpi.com/1420-3049/30/4/915tricarbonyl rhenium(I) complexplatinum(II) complextriimine ligandphotoluminescenceX-ray studieselectrochemistry |
| spellingShingle | Bartosz Zowiślok Anna Świtlicka Anna Maria Maroń Sławomir Kula Acetylenic Substituent: Influence on the Structure, Electrochemical, Photophysical, and Thermal Properties of Rhenium(I) and Platinum(II) Complexes Molecules tricarbonyl rhenium(I) complex platinum(II) complex triimine ligand photoluminescence X-ray studies electrochemistry |
| title | Acetylenic Substituent: Influence on the Structure, Electrochemical, Photophysical, and Thermal Properties of Rhenium(I) and Platinum(II) Complexes |
| title_full | Acetylenic Substituent: Influence on the Structure, Electrochemical, Photophysical, and Thermal Properties of Rhenium(I) and Platinum(II) Complexes |
| title_fullStr | Acetylenic Substituent: Influence on the Structure, Electrochemical, Photophysical, and Thermal Properties of Rhenium(I) and Platinum(II) Complexes |
| title_full_unstemmed | Acetylenic Substituent: Influence on the Structure, Electrochemical, Photophysical, and Thermal Properties of Rhenium(I) and Platinum(II) Complexes |
| title_short | Acetylenic Substituent: Influence on the Structure, Electrochemical, Photophysical, and Thermal Properties of Rhenium(I) and Platinum(II) Complexes |
| title_sort | acetylenic substituent influence on the structure electrochemical photophysical and thermal properties of rhenium i and platinum ii complexes |
| topic | tricarbonyl rhenium(I) complex platinum(II) complex triimine ligand photoluminescence X-ray studies electrochemistry |
| url | https://www.mdpi.com/1420-3049/30/4/915 |
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