Near-Unity Quantum Yields for Intersystem Crossing and Singlet Oxygen Generation in Polymethine-like Molecules: Design and Experimental Realization

• Published in: The journal of physical chemistry letters Vol. 1; no. 15; pp. 2354 - 2360
• Main Authors: Webster, Scott, Peceli, Davorin, Hu, Honghua, Padilha, Lazaro A, Przhonska, Olga V, Masunov, Artem E, Gerasov, Andriy O, Kachkovski, Alexey D, Slominsky, Yurii L, Tolmachev, Alexey I, Kurdyukov, Vladimir V, Viniychuk, Olexander O, Barrasso, Emma, Lepkowicz, Richard, Hagan, David J, Van Stryland, Eric W
• Format: Journal Article
• Language: English
• Published: American Chemical Society 05.08.2010
• Subjects: Molecular Structure, Quantum Chemistry, General Theory
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/jz100381v

The photophysical properties of two pairs of squaraine molecules where two oxygen atoms in a squaraine bridge are replaced with sulfur atoms are investigated. This substitution leads to an inversion of the lowest singlet π−π* electronic transition by an n−π* transition, effectively reducing the energy difference between singlet and triplet states and significantly increasing the intersystem crossing efficiency without the use of “heavy atoms”. Experimental results, in agreement with quantum chemical calculations, show near-unity values for triplet quantum yield and singlet oxygen generation quantum yield for sulfur-containing squaraines, which are potentially useful for two-photon photodynamic therapy.