The self-initiation of the thiol-ene coupling reaction of tetravinyl monomers containing main group elements and trivinyl heterocycles with alkyl and aryl dithiols resulted in the formation of highly cross-linked prepolymer gels which upon final curing at 120 degrees C yielded hard, monolithic polymeric materials. Because of the presence of highly polarizable main group elements such as Si, Ge, Sn, and S and the relative absence of highly electronegative elements, the resulting polymers exhibited high refractive indices ranging from 1.590 to 1.703 and Abbe numbers between 24.3 and 45.0. All of the polymers were highly transparent over the UV-vis region of the spectrum. Moreover, due to the high cross-linked density achievable in specific compositions, very hard materials capable of being ground and polished could be produced. The range of compositions produced yields important structure-property relationships, indicating the effect of monomer structure on mechanical and optical properties.