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σ-Pt-BODIPY Complexes with Platinum Attachment to Carbon Atoms C2 or C3 : Spectroscopic, Structural, and (Spectro)Electrochemical Studies and Photocatalysis

σ-Pt-BODIPY Complexes with Platinum Attachment to Carbon Atoms C2 or C3 : Spectroscopic, Structural, and (Spectro)Electrochemical Studies and Photocatalysis

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IRMLER, Peter, Rainer F. WINTER, 2018. σ-Pt-BODIPY Complexes with Platinum Attachment to Carbon Atoms C2 or C3 : Spectroscopic, Structural, and (Spectro)Electrochemical Studies and Photocatalysis. In: Organometallics. 37(2), pp. 235-253. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/acs.organomet.7b00806

@article{Irmler2018PtBOD-41185, title={σ-Pt-BODIPY Complexes with Platinum Attachment to Carbon Atoms C2 or C3 : Spectroscopic, Structural, and (Spectro)Electrochemical Studies and Photocatalysis}, year={2018}, doi={10.1021/acs.organomet.7b00806}, number={2}, volume={37}, issn={0276-7333}, journal={Organometallics}, pages={235--253}, author={Irmler, Peter and Winter, Rainer F.} }

2018-01-31T14:29:16Z 2018-01-31T14:29:16Z σ-Pt-BODIPY Complexes with Platinum Attachment to Carbon Atoms C2 or C3 : Spectroscopic, Structural, and (Spectro)Electrochemical Studies and Photocatalysis eng Irmler, Peter Irmler, Peter Winter, Rainer F. 2018 In this work we discuss five new complexes with the general formula trans-Pt(bodipy)I(PEt<sub>3</sub>)<sub>2</sub>, where differently substituted bodipy dyes attach to the coordination center via a direct Pt–C σ-bond to the pyrrolic carbon atom C2 or C3. We also report an isolable intermediate of the oxidative addition step where the bodipy is η<sup>2</sup>-bonded to the cis-Pt(0)(PEt<sub>3</sub>)<sub>2</sub> moiety. Comparison between the new complexes, meso-platinated analogue 8-Pt, and the parent dyes reveals that the site of platinum attachment influences the spectroscopic, photophysical, electrochemical, and electronic properties. In contrast to 8-Pt, absorption and emission bands are red-shifted with respect to the parent dyes. 2-Platinated bodipy dyes 2-Pt-6H, 2-Pt-6I, 2-Pt-Mes-6I, and 2-Pt-6Et exhibit dual fluorescence and NIR phosphorescence emissions, with low quantum yields, whereas 3-Pt emits solely by fluorescence (Φ<sup>Fl</sup> = 52.7%). The complexes are modestly efficient sensitizers for photochemical <sup>1</sup>O<sub>2</sub> production but outperform methylene blue. They also undergo one reversible one-electron reduction and oxidation as indicated by cyclic voltammetry. Half-wave potentials are cathodically shifted by 340–510 mV with respect to the parent dyes. The one-electron reduced and some of the one-electron oxidized forms were generated and investigated by UV/vis/NIR and EPR spectroscopy as well as TD-DFT calculations. The similarity of their spectra to those of the one-electron reduced or oxidized forms of other bodipy dyes as well as the richly structured EPR spectra and g-values close to g<sub>e</sub> attest to a dominant bodipy character of the relevant frontier MOs. Winter, Rainer F.

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