This study presents 13 new organic compounds with self-assembling behavior, which can be divided into two groups. The first synthesized group includes compounds based on 4′-(trifluoromethoxy)-[1,1′-biphenyl]-4-yl-4-(trifluoromethoxy) benzoate core, and the second includes compounds based on 4-((4-(trifluoromethoxy)phenyl)ethynyl)phenyl-4-(trifluoromethoxy) benzoate core. They differ in the number and location of the fluorine atom in the lateral position. Mesomorphic properties, phase transition enthalpies, refractive indices, birefringence, and MWIR (mid-wavelength infrared) spectral properties of the compounds were investigated, and the results were compared with currently used materials. The influence of the length of the core as well as type and position of substituents in the molecular core was analyzed. The lack of aliphatic protons in the molecular structure generated unique infrared properties.