Efficient intersystem crossing using singly halogenated carbomethoxyphenyl porphyrins measured using delayed fluorescence, chemical quenching, and singlet oxygen emission
Literature Information
Dawn M. Marin, Sonia Payerpaj, Graham S. Collier, Angy L. Ortiz, Gaurav Singh, Marcus Jones, Michael G. Walter
Sensitizers with high triplet quantum yields are useful for generating photovoltaics, photocatalysts and photodynamic therapy agents with increased efficiency. In this study, the heavy atom effect was used to optimize the triplet and singlet oxygen quantum yields of 5,10,15,20-tetrakis(4-carbomethoxyphenyl)porphyrin (1-TCM4PP). The triplet quantum yields, determined using delayed fluorescence, was calculated as 0.35 for 1-TCM4PP, 0.75 for 5,10,15-tris(4-carbomethoxyphenyl)-20-(4-bromophenyl)porphyrin (2-TBCM3PP) and 0.88 for 5,10,15-tris(4-carbomethoxyphenyl)-20-(4-iodophenyl)porphyrin (3-TCM3IPP). Chemical quenching of 1,3-diphenylisobenzofuran and singlet oxygen emission studies rendered an average singlet oxygen quantum yield of 0.51, 0.75, and 0.90 for TCM4PP, TBCM3PP and TCM3IPP respectively. These photophysical properties indicate that a single halogen atom is capable of transforming TCM4PP into a sensitizer with strong triplet character. This is useful for generating singlet oxygen for photodynamic therapy, creating a long lasting reactive species for catalysis and for extending diffusion lengths in photovoltaic applications while retaining three molecular modification points for further functionalization.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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