Negatively charged Ir(III) cyclometalated complexes containing a chelating bis-tetrazolato ligand: Synthesis, photophysics and the study of reactivity with electrophiles
The bis-tetrazolate dianion [1,2 BTB]2−, which is the deprotonated form of 1,2 bis-(1H-tetrazol-5-yl)benzene [1,2-H2BTB], is for the first time exploited as an ancillary N^N ligand for negatively charged [Ir(C^N)2(N^N)]−-type complexes, where C^N is represented by cyclometalated 2-phenylpyridine (pp...
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| Format: | Journal Article |
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R S C Publications
2016
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| Online Access: | http://purl.org/au-research/grants/arc/FT130100033 http://hdl.handle.net/20.500.11937/30736 |
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| author | Fiorini, V. Zacchini, S. Raiteri, Paolo Mazzoni, R. Zanotti, V. Massi, Massimiliano Stagni, S. |
| author_facet | Fiorini, V. Zacchini, S. Raiteri, Paolo Mazzoni, R. Zanotti, V. Massi, Massimiliano Stagni, S. |
| author_sort | Fiorini, V. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The bis-tetrazolate dianion [1,2 BTB]2−, which is the deprotonated form of 1,2 bis-(1H-tetrazol-5-yl)benzene [1,2-H2BTB], is for the first time exploited as an ancillary N^N ligand for negatively charged [Ir(C^N)2(N^N)]−-type complexes, where C^N is represented by cyclometalated 2-phenylpyridine (ppy) or 2-(2,4-difluorophenyl)pyridine (F2ppy). The new Ir(III) complexes [Ir(ppy)2(1,2 BTB)]− and [Ir(F2ppy)2(1,2 BTB)]− have been fully characterised and the analysis of the X-ray structure of [Ir(ppy)2(1,2 BTB)]− confirmed the coordination of the [1,2 BTB]2− dianion in a bis chelated fashion through the N-atoms adjacent to each of the tetrazolic carbons. Both of the new anionic Ir(III) complexes displayed phosphorescence in the visible region, with intense sky-blue (λmax = 460–490 nm) or aqua (λmax = 490–520 nm) emissions originating from [Ir(F2ppy)2(1,2 BTB)]− and [Ir(ppy)2(1,2 BTB)]−, respectively. In comparison with our very recent examples of anionic Ir(III)tetrazolate cyclometalates, the new Ir(III) tris chelate complexes [Ir(F2ppy)2(1,2 BTB)]− and [Ir(ppy)2(1,2 BTB)]−, display an improved robustness, allowing the study of their reactivity toward the addition of electrophiles such as H+ and CH3+. In all cases, the electrophilic attacks occurred at the coordinated tetrazolate rings, involving the reversible – by a protonation deprotonation mechanism – or permanent – upon addition of a methyl moiety – switching of their global net charge from negative to positive and, in particular, the concomitant variation of their photoluminescence output. The combination of the anionic complexes [Ir(F2ppy)2(1,2 BTB)]− or [Ir(ppy)2(1,2 BTB)]− with a deep red emitting (λmax = 686 nm) cationic Ir(III) tetrazole complex such as [IrTPYZ-Me]+, where TPYZ-Me is 2-(2-methyl-2H-tetrazol-5-yl)pyrazine, gave rise to two fully Ir(III)-based soft salts capable of displaying additive and O2-sensitive emission colours, with an almost pure white light obtained by the appropriate choice of the ionic components. |
| first_indexed | 2025-11-14T08:20:19Z |
| format | Journal Article |
| id | curtin-20.500.11937-30736 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T08:20:19Z |
| publishDate | 2016 |
| publisher | R S C Publications |
| recordtype | eprints |
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| spelling | curtin-20.500.11937-307362022-11-24T04:14:51Z Negatively charged Ir(III) cyclometalated complexes containing a chelating bis-tetrazolato ligand: Synthesis, photophysics and the study of reactivity with electrophiles Fiorini, V. Zacchini, S. Raiteri, Paolo Mazzoni, R. Zanotti, V. Massi, Massimiliano Stagni, S. The bis-tetrazolate dianion [1,2 BTB]2−, which is the deprotonated form of 1,2 bis-(1H-tetrazol-5-yl)benzene [1,2-H2BTB], is for the first time exploited as an ancillary N^N ligand for negatively charged [Ir(C^N)2(N^N)]−-type complexes, where C^N is represented by cyclometalated 2-phenylpyridine (ppy) or 2-(2,4-difluorophenyl)pyridine (F2ppy). The new Ir(III) complexes [Ir(ppy)2(1,2 BTB)]− and [Ir(F2ppy)2(1,2 BTB)]− have been fully characterised and the analysis of the X-ray structure of [Ir(ppy)2(1,2 BTB)]− confirmed the coordination of the [1,2 BTB]2− dianion in a bis chelated fashion through the N-atoms adjacent to each of the tetrazolic carbons. Both of the new anionic Ir(III) complexes displayed phosphorescence in the visible region, with intense sky-blue (λmax = 460–490 nm) or aqua (λmax = 490–520 nm) emissions originating from [Ir(F2ppy)2(1,2 BTB)]− and [Ir(ppy)2(1,2 BTB)]−, respectively. In comparison with our very recent examples of anionic Ir(III)tetrazolate cyclometalates, the new Ir(III) tris chelate complexes [Ir(F2ppy)2(1,2 BTB)]− and [Ir(ppy)2(1,2 BTB)]−, display an improved robustness, allowing the study of their reactivity toward the addition of electrophiles such as H+ and CH3+. In all cases, the electrophilic attacks occurred at the coordinated tetrazolate rings, involving the reversible – by a protonation deprotonation mechanism – or permanent – upon addition of a methyl moiety – switching of their global net charge from negative to positive and, in particular, the concomitant variation of their photoluminescence output. The combination of the anionic complexes [Ir(F2ppy)2(1,2 BTB)]− or [Ir(ppy)2(1,2 BTB)]− with a deep red emitting (λmax = 686 nm) cationic Ir(III) tetrazole complex such as [IrTPYZ-Me]+, where TPYZ-Me is 2-(2-methyl-2H-tetrazol-5-yl)pyrazine, gave rise to two fully Ir(III)-based soft salts capable of displaying additive and O2-sensitive emission colours, with an almost pure white light obtained by the appropriate choice of the ionic components. 2016 Journal Article http://hdl.handle.net/20.500.11937/30736 10.1039/c6dt02524b http://purl.org/au-research/grants/arc/FT130100033 http://purl.org/au-research/grants/arc/FT130100463 R S C Publications fulltext |
| spellingShingle | Fiorini, V. Zacchini, S. Raiteri, Paolo Mazzoni, R. Zanotti, V. Massi, Massimiliano Stagni, S. Negatively charged Ir(III) cyclometalated complexes containing a chelating bis-tetrazolato ligand: Synthesis, photophysics and the study of reactivity with electrophiles |
| title | Negatively charged Ir(III) cyclometalated complexes containing a chelating bis-tetrazolato ligand: Synthesis, photophysics and the study of reactivity with electrophiles |
| title_full | Negatively charged Ir(III) cyclometalated complexes containing a chelating bis-tetrazolato ligand: Synthesis, photophysics and the study of reactivity with electrophiles |
| title_fullStr | Negatively charged Ir(III) cyclometalated complexes containing a chelating bis-tetrazolato ligand: Synthesis, photophysics and the study of reactivity with electrophiles |
| title_full_unstemmed | Negatively charged Ir(III) cyclometalated complexes containing a chelating bis-tetrazolato ligand: Synthesis, photophysics and the study of reactivity with electrophiles |
| title_short | Negatively charged Ir(III) cyclometalated complexes containing a chelating bis-tetrazolato ligand: Synthesis, photophysics and the study of reactivity with electrophiles |
| title_sort | negatively charged ir(iii) cyclometalated complexes containing a chelating bis-tetrazolato ligand: synthesis, photophysics and the study of reactivity with electrophiles |
| url | http://purl.org/au-research/grants/arc/FT130100033 http://purl.org/au-research/grants/arc/FT130100033 http://hdl.handle.net/20.500.11937/30736 |