Near-Infrared-to-Visible Photon Upconversion Enabled by Conjugated Porphyrinic Sensitizers under Low-Power Noncoherent Illumination.
Published
Conference Paper
We report four supermolecular chromophores based on (porphinato)zinc(II) (PZn) and (polypyridyl)metal units bridged via ethyne connectivity (Pyr1RuPZn2, Pyr1RuPZnRuPyr1, Pyr1RuPZn2RuPyr1, and OsPZn2Os) that fulfill critical sensitizer requirements for NIR-to-vis triplet-triplet annihilation upconversion (TTA-UC) photochemistry. These NIR sensitizers feature: (i) broad, high oscillator strength NIR absorptivity (700 nm < λ(max(NIR)) < 770 nm; 6 × 10(4) M(-1) cm(-1) < extinction coefficient (λ(max(NIR))) < 1.6 × 10(5) M(-1) cm(-1); 820 cm(-1) < fwhm < 1700 cm(-1)); (ii) substantial intersystem crossing quantum yields; (iii) long, microsecond time scale T1 state lifetimes; and (iv) triplet states that are energetically poised for exergonic energy transfer to the molecular annihilator (rubrene). Using low-power noncoherent illumination at power densities (1-10 mW cm(-2)) similar to that of terrestrial solar photon illumination conditions, we demonstrate that Pyr1RuPZn2, Pyr1RuPZn2RuPyr1, and Pyr1RuPZnRuPyr1 sensitizers can be used in combination with the rubrene acceptor/annihilator to achieve TTA-UC: these studies represent the first examples whereby a low-power noncoherent NIR light source drives NIR-to-visible upconverted fluorescence centered in a spectral window within the bandgap of amorphous silicon.
Full Text
Duke Authors
Cited Authors
- Olivier, J-H; Bai, Y; Uh, H; Yoo, H; Therien, MJ; Castellano, FN
Published Date
- June 2015
Published In
Volume / Issue
- 119 / 22
Start / End Page
- 5642 - 5649
PubMed ID
- 25961428
Pubmed Central ID
- 25961428
Electronic International Standard Serial Number (EISSN)
- 1520-5215
International Standard Serial Number (ISSN)
- 1089-5639
Digital Object Identifier (DOI)
- 10.1021/acs.jpca.5b03199