We designed unique negative dielectric molecules, which were tricyclic compounds with a 5,5,6,6-tetrafluorocyclohexa-1,3-diene moiety in the mesogen, and then for the first time developed an effective synthetic protocol from commercially available 4-bromo-3,3,4,4-tetrafluorobut-1-ene. We also evaluated their physical properties for new mesogenic compounds, such as birefringence, dielectric anisotropy and shear viscosity, which are important characteristics for flat LC display device applications. The molecules clearly showed not only a large negative dielectric anisotropy and birefringence but also high viscosity.