Coordination polymers, especially metal-organic frameworks, have been one of fastest developing areas in materials science. Despite myriad applications, development of physical properties such as conductivity and magnetism, is comparatively slower due to the insulating nature of both metals and organic linkers. One successful strategy to address these shortcomings is to use sulfur-based linkers and metal-sulfur clusters, but this approach is limited to only a few systems and morphologies due to challenging synthesis. In the course of this thesis, I have discovered design principles which enable synthesis of a modular family of these materials. Furthermore, based on these well-defined materials, physical characterization demonstrates their interesting conductive, magnetic, optical and thermal properties, which show promising applications ranging from spintronics to energy applications. Chapter 2 outlines that redox-active Fe4S4 clusters can be connected with 1,4-benzenedithiolate to generate highly crystalline and soluble 1D-chains. Correspondingly, the conductivity can be tuned over a 104-fold range by redox control. Later, we were also able to isolate new Fe4S4-based polymers with methylated benzenedithiolates, the work of which is introduced in Chapter 3. Methylation results in the general trend of increasing electron-richness in the series, but the tetramethyl version exhibits unexpected properties arising from steric constraints. In addition to using sulfur-based nodes, a lot of my efforts have been devoted to developing new redox-active sulfur-linkers. A derivative of the well-known TTF core, tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFtt4−), is an attractive target. Chapter 4 illustrates the detailed synthesis and metalation of new TTFtt tin reagents, TTFtt(SnBu2)2 and its redox series. These serve as convenient precursors for the synthesis of other TTFtt4− metal complexes of varying charge states without additional post-synthetic oxidation. Followingly, Chapter 5 demonstrates that instead of group 10 metals, a diiron complex bridged by the doubly-oxidized TTFtt2− undergoes a thermally induced Fe-centered spin-crossover which yields significant diradical character on TTFtt2−. These molecular studies shed insights on new TTFtt chemistry motivates us to further explore its extended materials. Chapter 6 shows that using the doubly-oxidized TTFtt(SnBu2)22+ precursor, I have been able to generate neutral NiTTFtt chains with a precise composition. Surprisingly, these completely amorphous polymers exhibit record conductivity as pressed pellets (1280 S/cm) and detailed characterization suggests this is first intrinsic organic metal without any crystalline ordering. Beyond metallics, Chapter 7 demonstrates that using neutral TTFtt(SnBu2)2 leads to reduced NiTTFt chains, behaving typical p-type semiconductors. Furthermore, we also discovered high-performance photo-thermal electric conversion based on these polymers. Lastly, Chapter 8 summarizes some initial results about synthesis of MoS2-like coordination frameworks built with TTFtt and Mo3S7 clusters. Upon in situ oxidation, the conductivity of the resulting neutral framework can be increased to 0.2 S/cm. In addition, we have also begun work on the thin-film synthesis of these Mo-based materials. In short, this thesis presents two series of sulfur-based coordination materials, Fe4S4-based and TTFtt-based ones. With new synthesis strategies and ration designs, all reported materials display high compositional purity and, in many cases, crystallinity. These well-defined systems allow us to explore new chemistry and physics such as organic diradicals, metallics, photo-thermal electrical conversions.