3D coordination polymers of [2.2]paracyclophane and in situ silver(I) perfluoro-dicarboxylates: effects of the dicarboxylate spacers and conformations on the formation of complexes

Coordination polymers of [2.2]paracyclophane (pcp) with in situ silver(I) perfluoro-dicarboxylates characterized by single crystal X-ray analysis are described. Structures are found to strongly depend on the dicarboxylate spacer (n). With disilver(I) tetrafluorosuccinate ((CF2)n(COOAg)2, n = 2), 3D network with composition of [Ag4(pcp)(C2F4(CO2)2)2] (1) forms in which silver salts afford infinite double chains and pcp act as linkages between chains. Changing the silver salt to disilver hexafluoroglutarate ((CF2)n(COOAg)2, n = 3) produces 3D pillared-layer structure of composition of [Ag4(pcp)(C3F6(CO2)2)2] · THF (2) (THF = tetrahydrofuran), in which silver salts form 2D sheets and pcp act as pillars between the sheets. With silver octafluoroadipate (HO2C(CF2)nCO2Ag, n = 4), 2-fold interpenetrated diamond structure, [Ag2(pcp)2(HO2CC4F8CO2)2]2 · 2toluene (3), is obtained in which silver-anion chains and silver-pcp chains are connected with each other in the perpendicular manner. The three complexes represent unprecedented metal-organic networks of silver(I) multicarboxylates and polycyclic aromatic compounds. Additionally, the effects of the dicarboxylate conformations as well as the solvents on the resulting structures were discussed.