Dual ligand-based fluorescence and phosphorescence emission at room temperature from platinum thioxanthonyl complexes

Geist, Fabian; Jackel, Andrej; Winter, Rainer F.

Dual ligand-based fluorescence and phosphorescence emission at room temperature from platinum thioxanthonyl complexes

Dateien

Geist_0-274982.pdfGröße: 2.3 MBDownloads: 305

Datum

2015

Open Access-Veröffentlichung

Open Access Green

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

Publikationsstatus

Published

Erschienen in

Dalton Transactions. 2015, 44(9), pp. 3974-3987. ISSN 1477-9226. eISSN 1477-9234. Available under: doi: 10.1039/C4DT02410A

Zusammenfassung

New square-planar platinum(II) complexes of the type trans-[Pt(PEt₃)₂(Tx)(X)] (X = Br, Cl, I or CN) bearing a σ-bonded thioxanthon-2-yl (Tx) ligand have been prepared and characterised by X-ray crystallography, cyclic voltammetry, and by NMR and electronic absorption and luminescence spectroscopy. The ligand X hardly influences the electronic transitions, which indicates that the relevant molecular orbitals are largely confined to the Pt–Tx chromophore. In agreement with TD-DFT calculations the energetically lowest electronic transition is assigned as the Tx-centred π→π* HOMO → LUMO excitation. All four complexes display dual emission from the σ-bonded Tx ligand at ca. 450 nm and at ca. 510 nm, which are assigned as fluorescence originating from the ¹π*-state and as phosphorescence originating from the ³π*-state, respectively. The phosphorescence quantum yield increases with increasing σ-donor strength of the ligand X and reaches a uniquely high value of 18.8% for the chlorido complex Pt–Cl. Switching-on of Tx phosphorescence emission by the Pt(PEt₃)₂(X) fragment goes along with a reduction of the lifetime of the Tx triplet state from several ms in purely organic derivatives to ca. 2 μs in the complexes.

Fachgebiet (DDC)

540 Chemie

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ISO 690

GEIST, Fabian, Andrej JACKEL, Rainer F. WINTER, 2015. Dual ligand-based fluorescence and phosphorescence emission at room temperature from platinum thioxanthonyl complexes. In: Dalton Transactions. 2015, 44(9), pp. 3974-3987. ISSN 1477-9226. eISSN 1477-9234. Available under: doi: 10.1039/C4DT02410A

BibTex

@article{Geist2015ligan-29692,
  year={2015},
  doi={10.1039/C4DT02410A},
  title={Dual ligand-based fluorescence and phosphorescence emission at room temperature from platinum thioxanthonyl complexes},
  number={9},
  volume={44},
  issn={1477-9226},
  journal={Dalton Transactions},
  pages={3974--3987},
  author={Geist, Fabian and Jackel, Andrej and Winter, Rainer F.}
}

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    <dcterms:abstract xml:lang="eng">New square-planar platinum(II) complexes of the type trans-[Pt(PEt&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;(Tx)(X)] (X = Br, Cl, I or CN) bearing a σ-bonded thioxanthon-2-yl (Tx) ligand have been prepared and characterised by X-ray crystallography, cyclic voltammetry, and by NMR and electronic absorption and luminescence spectroscopy. The ligand X hardly influences the electronic transitions, which indicates that the relevant molecular orbitals are largely confined to the Pt–Tx chromophore. In agreement with TD-DFT calculations the energetically lowest electronic transition is assigned as the Tx-centred π→π* HOMO → LUMO excitation. All four complexes display dual emission from the σ-bonded Tx ligand at ca. 450 nm and at ca. 510 nm, which are assigned as fluorescence originating from the &lt;sup&gt;1&lt;/sup&gt;π*-state and as phosphorescence originating from the &lt;sup&gt;3&lt;/sup&gt;π*-state, respectively. The phosphorescence quantum yield increases with increasing σ-donor strength of the ligand X and reaches a uniquely high value of 18.8% for the chlorido complex Pt–Cl. Switching-on of Tx phosphorescence emission by the Pt(PEt&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;(X) fragment goes along with a reduction of the lifetime of the Tx triplet state from several ms in purely organic derivatives to ca. 2 μs in the complexes.</dcterms:abstract>
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