Supersonic jet expansions allow to cool molecules and to form molecular complexes over a wide range of expansion conditions, ranging from nearly effusive expansions of the pure vapour to colder expansions in carrier gases. The resulting molecular species can be probed by infrared absorption and Raman scattering. They are not in thermal equilibrium, but one can assign effective average Boltzmann temperatures for rotational, selected vibrational and in low-barrier cases even conformational degrees of freedom. If the conformational energy difference is not known, one can at least follow the evolution of competing structures with expansion conditions and from this derive relative energy sequences. For aminoethanol and its N-methylated variants, we explore rotational band contour analysis in OH stretching fundamentals, intensity analysis of sum and difference transitions with scaffold modes, relative intensities of isomers and the evolution of transient relative chirality to estimate the associated Boltzmann temperatures or energy sequences. The focus is on trends rather than on highly accurate numbers, which anyway depend on details like nozzle geometry or precise nozzle distance. These trends can be used for a better understanding of the vibrational spectra of other hydrogen-bonded systems. We show that the B3LYP functional is not able to describe the diastereomeric energy sequence for the dimethylaminoethanol dimer and that thermal shifts of infrared bands due to the weakening of hydrogen bonding depend strongly on the hydrogen bond strain. We also discuss high-barrier cases of conformational isomerism, which resist supersonic cooling and allow for low-temperature spectroscopy of metastable isomers. We assign the OH stretching spectra of the monohydrate of dimethylaminoethanol with an unusually strong water downshift. Finally, one of the successful machine learning-based models of the first HyDRA blind challenge is applied and improved for predicting the position of its water OH stretch wavenumber. The original model, based on computed harmonic wavenumbers for moderately strong H-bonds leads to a difference of 461 cm⁻¹ whereas improvements based on VPT2 calculations for the base model reduce this to 49 cm⁻¹.