Annulated, hexapyrrolic anti-aromatic rosarin, a β,β′-two-carbon bridged-(1.0.1.0.1.0)hexaphyrin derivatives are Huckel’s 24π antiaromatic system. These are also known to form stable one-electron reduced species 25π species upon exposure to the multiple protons. However, the general synthesis of peripherally substituted analogues were hurdled due to the difficulties of the accessibility of the key building blocks. With this presentation, we report the synthesis of new building blocks that can lead to the peripherally substituted hexapyrrolic rosarins. The properties of the corresponding new rosarians including redox properties, spectroscopic properties and protonation behavior will be presented. The redox chemistry and protonation behavior of the unsubstituted rosarian and peripherally substituted analogues will be systematically compared. The time-dependent spectral changes after addition of excess acids indicates that the single electron reduction is faster in hexa-fluoro substituted one compared with the unsubstituted one. Slightly increased reduction potential of substituted rosarian and the electron withdrawing nature of fluoride exhibited dramatically different properties. Detailed studies will be presented.