Intramolecular Charge Transfer and Spin-Orbit Coupled Intersystem Crossing in Hypervalent Phosphorus(V) and Antimony(V) Porphyrin Black Dyes.

Autor:	Hamza JR; Department of Chemistry & Biochemistry, University of Minnesota Duluth, Duluth, Minnesota 55812, United States., Sharma JK; Department of Chemistry, University of North Texas, Denton, Texas 76203-5017, United States., Karr PA; Department of Physical Sciences and Mathematics, Wayne State College, 1111 Main Street, Wayne, Nebraska 68787, United States., van der Est A; Department of Chemistry, Brock University, St. Catharines, Ontario L2S 3A1, Canada., D'Souza F; Department of Chemistry, University of North Texas, Denton, Texas 76203-5017, United States., Poddutoori PK; Department of Chemistry & Biochemistry, University of Minnesota Duluth, Duluth, Minnesota 55812, United States.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2024 Sep 18; Vol. 146 (37), pp. 25403-25408. Date of Electronic Publication: 2024 Sep 09.
DOI:	10.1021/jacs.4c06674
Abstrakt:	Porphyrin dyes with strong push-pull type intramolecular charge transfer (ICT) character and broad absorption across the visible spectrum are reported. This combination of properties has been achieved by functionalizing the periphery of hypervalent and highly electron-deficient phosphorus(V) and antimony(V) centered porphyrins with electron-rich triphenylamine (TPA) groups. As a result of the large difference in electronegativity between the porphyrin ring and the peripheral groups, their absorption profiles show several strong charge transfer transitions, which in addition to the porphyrin-centered π → π* transitions, make them panchromatic black dyes with high absorption coefficients between 200 and 800 nm. Time-resolved optical and electron paramagnetic resonance (EPR) studies show that the lowest triplet state also has ICT character and is populated by spin-orbit coupled intersystem crossing.
Databáze:	MEDLINE
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