Electron-deficient near-infrared Pt(II) and Pd(II) benzoporphyrins with dual phosphorescence and unusually efficient thermally activated delayed fluorescence: First demonstration of simultaneous oxygen and temperature sensing with a single emitter

P.W. Zach, S.A. Freunberger, I. Klimant, S.M. Borisov, ACS Applied Materials & Interfaces 9 (2017) 38008–38023.

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Journal Article | Published | English
Author
Zach, Peter W.; Freunberger, Stefan AlexanderIST Austria ; Klimant, Ingo; Borisov, Sergey M.
Abstract
We report a family of Pt and Pd benzoporphyrin dyes with versatile photophysical properties and easy access from cheap and abundant chemicals. Attaching 4 or 8 alkylsulfone groups onto a meso-tetraphenyltetrabenzoporphyrin (TPTBP) macrocylcle renders the dyes highly soluble in organic solvents, photostable, and electron-deficient with the redox potential raised up to 0.65 V versus the parent porphyrin. The new dyes intensively absorb in the blue (Soret band, 440–480 nm) and in the red (Q-band, 620–650 nm) parts of the electromagnetic spectrum and show bright phosphorescence at room-temperature in the NIR with quantum yields up to 30% in solution. The small singlet–triplet energy gap yields unusually efficient thermally activated delayed fluorescence (TADF) at elevated temperatures in solution and in polymeric matrices with quantum yields as high as 27% at 120 °C, which is remarkable for benzoporphyrins. Apart from oxygen sensing, these properties enable unprecedented simultaneous, self-referenced oxygen and temperature sensing with a single indicator dye: whereas oxygen can be determined either via the decay time of phosphorescence or TADF, the temperature is accessed via the ratio of the two emissions. Moreover, the dyes are efficient sensitizers for triplet–triplet annihilation (TTA)-based upconversion making possible longer sensitization wavelength than the conventional benzoporphyrin complexes. The Pt-octa-sulfone dye also features interesting semireversible transformation in basic media, which generates new NIR absorbing species.
Publishing Year
Date Published
2017-10-10
Journal Title
ACS Applied Materials & Interfaces
Volume
9
Issue
43
Page
38008-38023
ISSN
eISSN
IST-REx-ID

Cite this

Zach PW, Freunberger SA, Klimant I, Borisov SM. Electron-deficient near-infrared Pt(II) and Pd(II) benzoporphyrins with dual phosphorescence and unusually efficient thermally activated delayed fluorescence: First demonstration of simultaneous oxygen and temperature sensing with a single emitter. ACS Applied Materials & Interfaces. 2017;9(43):38008-38023. doi:10.1021/acsami.7b10669
Zach, P. W., Freunberger, S. A., Klimant, I., & Borisov, S. M. (2017). Electron-deficient near-infrared Pt(II) and Pd(II) benzoporphyrins with dual phosphorescence and unusually efficient thermally activated delayed fluorescence: First demonstration of simultaneous oxygen and temperature sensing with a single emitter. ACS Applied Materials & Interfaces, 9(43), 38008–38023. https://doi.org/10.1021/acsami.7b10669
Zach, Peter W., Stefan Alexander Freunberger, Ingo Klimant, and Sergey M. Borisov. “Electron-Deficient near-Infrared Pt(II) and Pd(II) Benzoporphyrins with Dual Phosphorescence and Unusually Efficient Thermally Activated Delayed Fluorescence: First Demonstration of Simultaneous Oxygen and Temperature Sensing with a Single Emitter.” ACS Applied Materials & Interfaces 9, no. 43 (2017): 38008–23. https://doi.org/10.1021/acsami.7b10669.
P. W. Zach, S. A. Freunberger, I. Klimant, and S. M. Borisov, “Electron-deficient near-infrared Pt(II) and Pd(II) benzoporphyrins with dual phosphorescence and unusually efficient thermally activated delayed fluorescence: First demonstration of simultaneous oxygen and temperature sensing with a single emitter,” ACS Applied Materials & Interfaces, vol. 9, no. 43, pp. 38008–38023, 2017.
Zach PW, Freunberger SA, Klimant I, Borisov SM. 2017. Electron-deficient near-infrared Pt(II) and Pd(II) benzoporphyrins with dual phosphorescence and unusually efficient thermally activated delayed fluorescence: First demonstration of simultaneous oxygen and temperature sensing with a single emitter. ACS Applied Materials & Interfaces. 9(43), 38008–38023.
Zach, Peter W., et al. “Electron-Deficient near-Infrared Pt(II) and Pd(II) Benzoporphyrins with Dual Phosphorescence and Unusually Efficient Thermally Activated Delayed Fluorescence: First Demonstration of Simultaneous Oxygen and Temperature Sensing with a Single Emitter.” ACS Applied Materials & Interfaces, vol. 9, no. 43, ACS, 2017, pp. 38008–23, doi:10.1021/acsami.7b10669.
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