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Five new bi- and trimetallic copper-organosilsesquioxanes {[VinSiO2]12­Cu4Cs4­(BuOH)2­(EtOH)2­(MeOH)}­·2BuOH (1), {[PhSiO2]12­Cu4Cs2K2­(1,4-dioxane)9­(H2O)2}­·3.4­(1,4-dioxane) (2), {[PhSiO2]12­Cu4Cs4­(DMF)6}­·2DMF (3), {[MeSiO2]12­Cu4Cs4(THF)4.5­(MeOH)2­(H2O)0.25} (4), and {[MeSiO2]24­Cu10Cs6­(OH)2­(THF)4.2­(MeOH)4.1­(H2O)0.7} (5) have been synthesized by an exchange reaction between discrete cage alkali,copper-siloxane and cesium chloride (1, 2) or cesium carbonate (4, 5) or by interaction of copper-phenylsiloxane with cesium phenylsiloxanolate (3). While in 1–4 the alkali,copper-silsesquioxane cage remains stable during reaction procedures, complex 5 was obtained by unexpected dimerization of two cages. The neutral cages act with solvent molecules and neighboring cages as square (1, 3, 5), tetrahedral (4), or octahedral (2) nodes giving, respectively, the two-periodic (2D) sql net, and the three-periodic (3D) dia or pcu nets. The roles of the cage structure, nature of metal atoms, and organic coating in the formation of one-, two-, and three-periodic coordination polymers are discussed in the example of newly synthesized and previously obtained alkali,copper-organosiloxanes and copper-organosiloxanes with sandwich or globular cage structures. What’s more, the charge distribution in crystals of 1–3 was analyzed by means of Bader’s Quantum Theory of Atoms-in-Molecules approach giving evidence of relatively strong bonding between neighboring cages.

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