Hydrothermal reaction of Cu(MeCO2)(2), (4-pyddylthio)acetic acid and NH4SCN resulted in a twelve-connected face-centered cubic topological metal-organic framework [Cu-3(pdt)(2)(CN)] (pdt = pyridinethiolate) in which Cu6S4 clusters act as twelve-connected nodes and pyridine rings and cyanides act as connectors. As an extension, an unprecedented fourteen-connected body-centered cubic coordination polymer [Cu19I4(pdt)(12)(SH)(3)] has been synthesized by three methods, in which nanosized chiral Cu19I4S12 Clusters act as fourteen-connected nodes and triple pyridine rings and hydrosulfides act as connectors. The in situ S-C(sp(3)), S-C(sp(2)), and S-C(sp) cleavage reactions have been observed in the work.