Synthesis of new cyclotetrasiloxane scaffolds containing peripherally functionalized 3-pyridyl moieties, [MeSiO(CH=(CHPy)-Py-3)](4) (L-1) and [MeSiO((CH2CH2Py)-Py-3)](4) (L-2), and their reactivity studies with certain d(10) metal ions are reported. The ligand L-1 is obtained by the Heck-coupling reaction of tetramethyl tetravinyl tetrasiloxane (D-4(vi)) and 3-bromopyridine in the presence of the Pd(0) catalysts. The as-synthesized ligand L-1 shows the presence of three stereoisomers, cis-trans-cis (L-1A), cis-cis-trans (L-1B), and all-trans (L-1C), which are quantitatively separated by column chromatography. Subsequent reduction of L-1A, L-1B, and L-1C with triethylsilane in the presence of catalytic amounts of Pd/C leads to the formation of the ligands L-2A, L-2B, and L-2C with retention of stereochemistry due to the precursor moieties. Treatment of ZnI2 with L-1A gives a one-dimensional coordination framework [(L-1A)(4)(ZnI2)(2)](infinity), 1. These 1D-chains are further connected by pi-pi stacking interactions between the pyridyl groups of the adjacent chains leading to the formation of a three-dimensional network with the topology of a PtS net. The reaction of silver nitrate with ligand L-1B gives a chain like one-dimensional cationic coordination polymer {[(L-1B)(4)Ag-2]center dot 2NO(3)center dot H2O center dot CH3OH }(infinity), 2, consisting of two different kinds of 32-membered macrocycles. Treatment of the all-trans ligand L-2C with copper(I) iodide salt results in the formation of a cubane-type Cu4I4 cluster MOF [(L-2C)(4)Cu4I4](infinity), 3, in a two-dimensional 4-connected uninodal sql/Shubnikov tetragonal plane net topology represented by the Schlafli symbol {4(4).6(2)}. This MOF displays a thermochromic luminescence behavior due to Cu4I4 clusters showing an orange emission at 298 K and a blue emission at 77 K.