Photophysical Study on the Rigid Pt(II) Complex [Pt(naphen)(Cl)] (Hnaphen = Naphtho[1,2-b][1,10]Phenanthroline and Derivatives
dc.bibliographicCitation.firstPage | 7022 | |
dc.bibliographicCitation.issue | 20 | |
dc.bibliographicCitation.volume | 27 | |
dc.contributor.author | Krause, Maren | |
dc.contributor.author | Maisuls, Iván | |
dc.contributor.author | Buss, Stefan | |
dc.contributor.author | Strassert, Cristian A. | |
dc.contributor.author | Winter, Andreas | |
dc.contributor.author | Schubert, Ulrich S. | |
dc.contributor.author | Nair, Shruthi S. | |
dc.contributor.author | Dietzek-Ivanšić, Benjamin | |
dc.contributor.author | Klein, Axel | |
dc.date.accessioned | 2023-02-06T07:28:17Z | |
dc.date.available | 2023-02-06T07:28:17Z | |
dc.date.issued | 2022 | |
dc.description.abstract | The electrochemistry and photophysics of the Pt(II) complexes [Pt(naphen)(X)] (Hnaphen = naphtho[1,2-b][1,10]phenanthroline, X = Cl or C≡CPh) containing the rigid tridentate C^N^N-coordinating pericyclic naphen ligand was studied alongside the complexes of the tetrahydro-derivative [Pt(thnaphen)(X)] (Hthnaphen = 5,6,8,9-tetrahydro-naphtho[1,2-b][1,10]phenanthroline) and the N^C^N-coordinated complex [Pt(bdq)(Cl)] (Hbdq = benzo[1,2-h:5,4-h’]diquinoline. The cyclic voltammetry showed reversible reductions for the C^N^N complexes, with markedly fewer negative potentials (around −1.6 V vs. ferrocene) for the complexes containing the naphen ligand compared with the thnaphen derivatives (around −1.9 V). With irreversible oxidations at around +0.3 V for all of the complexes, the naphen made a difference in the electrochemical gap of about 0.3 eV (1.9 vs. 2.2 eV) compared with thnaphen. The bdq complex was completely different, with an irreversible reduction at around −2 V caused by the N^C^N coordination pattern, which lacked a good electron acceptor such as the phenanthroline unit in the C^N^N ligand naphen. Long-wavelength UV-Vis absorption bands were found around 520 to 530 nm for the C^N^N complexes with the C≡CPh coligand and were red-shifted when compared with the Cl derivatives. The N^C^N-coordinated bdq complex was markedly blue-shifted (493 nm). The steady-state photoluminescence spectra showed poorly structured emission bands peaking at around 630 nm for the two naphen complexes and 570 nm for the thnaphen derivatives. The bdq complex showed a pronounced vibrational structure and an emission maximum at 586 nm. Assuming mixed 3LC/3MLCT excited states, the vibronic progression for the N^C^N bdq complex indicated a higher LC character than assumed for the C^N^N-coordinated naphen and thnaphen complexes. The blue-shift was a result of the different N^C^N vs. C^N^N coordination. The photoluminescence lifetimes and quantum yields ΦL massively increased from solutions at 298 K (0.06 to 0.24) to glassy frozen matrices at 77 K (0.80 to 0.95). The nanosecond time-resolved study on [Pt(naphen)(Cl)] showed a phosphorescence emission signal originating from the mixed 3LC/3MLCT with an emission lifetime of around 3 µs. | eng |
dc.description.version | publishedVersion | eng |
dc.identifier.uri | https://oa.tib.eu/renate/handle/123456789/11235 | |
dc.identifier.uri | http://dx.doi.org/10.34657/10271 | |
dc.language.iso | eng | |
dc.publisher | Basel : MDPI | |
dc.relation.doi | https://doi.org/10.3390/molecules27207022 | |
dc.relation.essn | 1420-3049 | |
dc.relation.ispartofseries | Molecules : a journal of synthetic chemistry and natural product chemistry 27 (2022), Nr. 20 | |
dc.rights.license | CC BY 4.0 Unported | |
dc.rights.uri | https://creativecommons.org/licenses/by/4.0 | |
dc.subject | cyclometalation | eng |
dc.subject | pericyclic ligands | eng |
dc.subject | photoluminescence | eng |
dc.subject | platinum | eng |
dc.subject | time-resolved | eng |
dc.subject.ddc | 540 | |
dc.title | Photophysical Study on the Rigid Pt(II) Complex [Pt(naphen)(Cl)] (Hnaphen = Naphtho[1,2-b][1,10]Phenanthroline and Derivatives | eng |
dc.type | article | |
dc.type | Text | |
dcterms.bibliographicCitation.journalTitle | Molecules : a journal of synthetic chemistry and natural product chemistry | |
tib.accessRights | openAccess | |
wgl.contributor | IPHT | |
wgl.subject | Chemie | ger |
wgl.type | Zeitschriftenartikel | ger |
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