New bowl-shaped (bowlic) liq. crystals with rigid W-oxo calix[4]arene (I; Z = N:NC6H2-3,4-(O(CH2)12H)2-5-R where R = H, O(CH2)12H) based mesogens 1a and 1b, resp., are reported. These compds. exhibit discotic columnar phases which are stable over approx. a 200° temp. range. The uncomplexed tetra-phenol ligand displays only a transient mesophase on the first heating, and the conformational rigidity provided through W-oxo complexation is necessary for well behaved mesomorphism. For 1a, the clearing point is at 320° which leads to decompn. in the isotropic phase. The addn. of 4 more sidechains to form 1b results in a lower clearing point (267°) and a stable isotropic phase. Polarized optical microscopy and DSC indicate that 1b displays a bowlic Dho phase (also known as PA or Bho), whereas studies on 1a's mesophase were less definitive. Both 1a and 1b exhibit a pronounced tendency to bind Lewis base guests in their cavities, and DMF forms very strong complexes which were spectroscopically characterized. The DMF guest produces large effects on the phase behavior by suppressing mesomorphism and lowering the isotropic points of 1a and 1b to 115 and 84°, resp. This extreme sensitivity of the DMF guest suggests that the mols. organize in head-to-tail structures in the mesophases and that the W-oxo group of one mol. protrudes into the cavity of the neighboring mol. [on SciFinder(R)]