Rotational tunneling of monodeuterated methyl groups of dimethyl-s-tetrazine guest molecules in n-octane and tetramethylbenzene crystalline matrices is characterized by optical spectroscopy including hole burning methods. An analysis of the level structure shows that the asymmetric substitution leads to a partial localization of one of the methyl groups in n-octane, while in the tetramethylbenzene host both groups are equivalent and are strongly localized. The relaxation, by incoherent tunneling, between different orientations proceeds on a time scale of > 10(7) s(-1) in n-octane at temperatures below 2 K. The coupling of the orientation of the methyl group with the environment is estimated from information on inhomogeneous broadening attributed to random strain fields in the crystal. The strength of this coupling is related to the observed relaxation behavior. The origin of the asymmetry of the rotational potential is discussed in terms of static and dynamic contributions which are due to changes of bond length upon isotopic substitution and the dependence of vibrational frequencies on orientation.