Coexistence of Jahn–Teller minima resulting from the coupling to different accepting modes within the adiabatic potential energy surface (APES) is not possible within the framework of linear vibronic coupling theory. For the lowest exited triplet state T1u3 of inorganic complexes with s2 electronic ground-state configuration, such a coexistence, due to quadratic coupling effects, is discussed. As a direct experimental evidence two vibronic progressions with different accepting modes in the emission spectra resulting from a single electronic state are observed in the emission spectra of the title compounds. The observation of vibronic finestructure in the emission spectra of [TeCl6]2− is reported for the first time.