Photochemical and chemical reduction of pyrylium salts in THF solution gave their corresponding radicals which were in equilibrium with dimers. The quantum yields for raidcal formation and the standard enthalpy change ΔH0 for dimerization decrease with increasing the electron-donating character of the substituting groups in the pyrylium ring. Specially, ΔH0 for pentaphenylpyranyl and pentaphenylthiopyranyl
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