Conventional and linear-polarized IR-spectroscopic tools based on reducing-difference procedures for non-polarized and polarized IR-spectra interpretation as well as orientation technique of solids (colloidal suspension in nematic liquid crystal) and UV/vis spectroscopy are applied for investigation of new sol-gel materials with potential optical application of doped organic dye 3-(3-(4-(dimethylamino)phenyl)propenoyl)-2H-chromen-2-one (K2) and Sm3+ ions. The results show that during aging of the monoliths Sm3+ forms an unstable complex with K2, [Sm(K2)(2)(H2O2](NO3)(3), which transforms to [Sm(H2O)(6)](3+) one, typical for gel-Sm3+ system. Quantum chemical ab initio and DFT calculations are reported with a view to support experimental IR-characteristic bands of the system studied.