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Photochemical upconversion is a process whereby two lower-energy photons are converted into a higher-energy photon by sensitized triplet-triplet annihilation. While recent interest in this process has been motivated by improving the efficiencies of solar cells, many applications are being explored. In this review, we address the underlying physicochemical phenomena that are responsible for photochemical upconversion. We review their kinetics, and the requirements for annihilators and sensitizers to design efficient upconversion systems. We discuss the spin physics of the bi-excitonic interactions and how the spin character of the triplet pairs can fundamentally limit the upconversion efficiency and give rise to the magnetic field effect on delayed photoluminescence. Finally, we address light-matter coupling phenomena that could be employed to enhance photochemical upconversion.
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http://dx.doi.org/10.1146/annurev-physchem-092722-104952 | DOI Listing |
Chem Commun (Camb)
August 2025
Hefei National Research Center for Physical Sciences at the Microscale, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China.
Nitric oxide (NO) is a pivotal signaling molecule whose therapeutic potential is constrained by challenges in controlled delivery. Photocontrolled strategies employing red to near-infrared (NIR) light, known for deep tissue penetration and minimal phototoxicity, present transformative opportunities for spatiotemporally precise NO release. This review surveys emerging red/NIR-activated NO release platforms and elucidates core photochemical strategies, including direct red/NIR absorption by engineered NO donors, upconversion nanoparticles (UCNPs), two-photon excitation, and photoredox catalysis.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland.
Photoactive Cr complexes are typically based on polypyridine coordination environments, exhibit red luminescence, and are good photo-oxidants but have modest photoreducing properties. We report new Cr complexes with anionic chelate ligands that enable color-tunable near-infrared luminescence and red-light-driven photoreduction reactions involving elementary steps that are endergonic up to 0.5 eV.
View Article and Find Full Text PDFMolecules
May 2025
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Coupling organic light-harvesting materials with lead halide perovskite quantum dots (LHP QDs) is an attractive approach that could provide great potential in optoelectronic applications owing to the diversity of organic materials available and the intriguing optical and electronic properties of LHP QDs. Here, we demonstrate energy collection by CsPbI QDs from a near-infrared (NIR) light-harvesting upconversion system. The upconversion system consists of Pd-tetrakis-5,10,15,20-(p-methoxycarbonylphenyl)-tetraanthraporphyrin (PdTAP) as the sensitizer to harvest NIR photons and rubrene as the annihilator to generate upconverted photons via triplet fusion.
View Article and Find Full Text PDFSci Adv
April 2025
Department of Chemical Biology, School of Chemistry and Chemical Engineering and Institute of Translational Medicine, Shanghai Jiao Tong University, Shanghai 200240, China.
Photochemical afterglow materials have drawn considerable attention due to their attractive luminescent properties and great application potential. Considering the classical photochemical afterglow materials always exhibit poor luminescence, it is urgent to gain fundamental understanding of the main limiting factors. Here, we identified the existence of a dark-state triplet in the photochemical process, and an overwhelming percentage of ~98.
View Article and Find Full Text PDFChemistry
May 2025
School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, P. R. China.
Photochemical deoxygenation offers a promising solution to the oxygen sensitivity issue in Triplet-triplet annihilation upconversion (TTA-UC). This study utilized polyethylene glycol (PEG)-200 and polyethylene glycol diacrylate (PEGDA)-575 as solvents and singlet oxygen scavengers for TTA-UC conducted in air. The upconversion efficiency of Pt(OEP)/DPA in aerated PEG-200 is similar to that in nitrogen-saturated PEG-200.
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