A series of new dicationic sensitizers that are hybrids of pyrylium salts and viologens has been synthesized. The electrochemical and photophysical properties of these “pyrylogen” sensitizers are reported in sufficient detail to allow rationale design of new photoinduced electron transfer reactions. The range of their reduction potentials (+0.37–+0.05 V vs SCE) coupled with their range of singlet (48–63 kcal mol⁻¹) and triplet (48–57 kcal mol⁻¹) energies demonstrate that they are potent oxidizing agents in both their singlet and triplet excited states, thermodynamically capable of oxidizing substrates with oxidation potentials as high as 3.1 eV. The pyrylogens are synthesized in three steps from readily available starting materials in modest overall 11.4–22.3% yields. These sensitizers have the added advantages that: (1) their radical cations do not react on the CV timescale with oxygen bypassing the need to run reactions under nitrogen or argon and (2) have long wavelength absorptions between 413 and 523 nm well out of the range where competitive absorbance by most substrates would cause a problem. These new sensitizers do react with water requiring special precautions to operate in a dry reaction environment.

The first three examples of the thioanalog of the 4,2′-pyrylogen ring system are reported. The influence of the sulfur atom on the structural, electrochemical, and photophysical behavior of this ring system is discussed. In addition, these 4,2′-thiopyrylogens are compared to their previously reported 4,4′-isomers and their 4,4′- and 4,2′-oxygen analogs. Copyright © 2010 John Wiley & Sons, Ltd.