This article describes efforts toward the development of a new core for calamitic mesogens based upon the introduction of an extended heteroaromatic boron-containing ring. A series of tri-catenar mesogenic boronate ester derivatives of the 2-phenyl-1,3,2-benzodioxaborole has been synthesized and characterized. The flat central core appeared to be a suitable feature for these derivatives to support anisotropic alignment. Additionally, these derivatives should possess an inherent dipole in the core. However, thermal analysis (polarized optical microscopy and differential scanning calorimetry) did not reveal any mesophases.