Directing Energy Transfer in Panchromatic Platinum Complexes for Dual Vis–Near-IR or Dual Visible Emission from σ-Bonded BODIPY Dyes

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2017
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Malzkuhn, Sabine
Kuss-Petermann, Martin
Wenger, Oliver
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Inorganic Chemistry. 2017, 56(2), pp. 914-930. ISSN 0020-1669. eISSN 1520-510X. Available under: doi: 10.1021/acs.inorgchem.6b02549
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We report on the platinum complexes trans-Pt(BODIPY)(8-ethynyl-BODIPY)(PEt3)2 (EtBPtB) and trans-Pt(BODIPY)(4-ethynyl-1,8-naphthalimide)(PR3)2 (R = Et, EtNIPtB-1; R = Ph, EtNIPtB-2), which all contain two different dye ligands that are connected to the platinum atom by a direct σ bond. The molecular structures of all complexes were established by X-ray crystallography and show that the different dye ligands are in either a coplanar or an orthogonal arrangement. π-stacking and several CH···F and short CH···π interactions involving protons at the phosphine substituents lead to interesting packing motifs in the crystal. The complexes feature several strong absorptions (ε = 3.2 × 105–5.5 × 105 M–1 cm–1) that cover the regime from 350 to 480 nm (EtNIPtB-1 and EtNIPtB-2) or from 350 to 580 nm (EtBPtB). Besides the typical absorption bands of both kinds of attached dyes, they also feature an intense band near 400–420 nm, which is assigned by time-dependent density functional theory calculations to a higher-energy transition within the ethynyl-BODIPY (EtB) ligand or to charge transfer between the BODIPY (B) and naphthalimide (NI) chromophores. All complexes show dual fluorescence and phosphorescence emission from either the B (EtNIPtB-1 and EtNIPtB-2) or EtB (EtBPtB) ligand with a maximum phosphorescence quantum yield of 41% for EtNIPtB-1. The latter seems to be the highest reported value for room temperature phosphorescence from a BODIPY dye. The complete quenching of the emission from the chromophore absorbing at the higher energy and the appearance of the corresponding absorption bands in the fluorescence and phosphorescence excitation spectra indicate complete and rapid energy transfer to the chromophore with the lower-energy excited state, i.e., EtNI → B in EtNIPtB-1 and EtNIPtB-2 and B → EtB in EtBPtB. The latter process was further investigated by transient absorption spectroscopy, indicating that energy transfer is complete within 0.6 ns. EtNIPtB-1 catalyzes the photooxidation of 1,5-dihydroxynaphthalene with photogenerated 1O2 to Juglone at a much faster rate than methylene blue but with only modest quantum yields of 37% and with the onset of photodegradation after 60 min.

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ISO 690GEIST, Fabian, Andrej JACKEL, Peter IRMLER, Michael LINSEIS, Sabine MALZKUHN, Martin KUSS-PETERMANN, Oliver WENGER, Rainer F. WINTER, 2017. Directing Energy Transfer in Panchromatic Platinum Complexes for Dual Vis–Near-IR or Dual Visible Emission from σ-Bonded BODIPY Dyes. In: Inorganic Chemistry. 2017, 56(2), pp. 914-930. ISSN 0020-1669. eISSN 1520-510X. Available under: doi: 10.1021/acs.inorgchem.6b02549
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@article{Geist2017-01-17Direc-37284,
  year={2017},
  doi={10.1021/acs.inorgchem.6b02549},
  title={Directing Energy Transfer in Panchromatic Platinum Complexes for Dual Vis–Near-IR or Dual Visible Emission from σ-Bonded BODIPY Dyes},
  number={2},
  volume={56},
  issn={0020-1669},
  journal={Inorganic Chemistry},
  pages={914--930},
  author={Geist, Fabian and Jackel, Andrej and Irmler, Peter and Linseis, Michael and Malzkuhn, Sabine and Kuss-Petermann, Martin and Wenger, Oliver and Winter, Rainer F.}
}
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