Synthesis and Physical Chemistry of s-Tetrazines: Which Ones are Fluorescent and Why?

New fluorescent tetrazines have been prepared and their electrochemistry and fluorescence efficiency evaluated. The occurrence of fluorescence as well as the wavelength were found to be strongly dependent on the substituents, which have to be electronegative heteroatoms. This has been rationalized through a computational study that showed that the crucial factor is the nature of the HOMO, which determines the existence or not of fluorescence. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) New s‐tetrazines have been synthesized and their electrochemical and photophysical properties investigated. Their electronic properties were rationalized by DFT calculations affording a predictive tool for the occurrence or not of fluorescence in this class of compounds.