Silver(I) Coordination Polymers of 2,11-Dithia[3.3]paracyclophane and in situ Silver(I) Perfluoro-dicarboxylates

Coordination polymers of 2,11‐dithia[3.3]paracyclopane (dtpcp) with in situ silver(I) perfluoro‐dicarboxylates characterized by single crystal X‐ray analysis are described. Their structures were found to strongly depend on the dicarboxylates. With disilver(I) tetrafluoro‐succinate [(CF2)n(COOAg)2, n=2], a 1D chain of [Ag4(dtpcp)3‐ (C2F4(CO2)2)2]·2CH3OH (1) forms in which two silver(I) ions link with two dtpcp ligands to afford a four‐numbered ring and disilver(I) tetrafluoro‐succinates link such rings. Changing the silver salt to disilver(I) hexafluoroglutarate [(CF2)n(COOAg)2, n=3] produces a 3D structure with composition of [Ag2(dtpcp)(C3F6(CO2)2)] (2), in which the disilver(I) hexafluoroglutarates connect with each other to form a 1D S‐shape chain and dtpcp ligands bridge such chains to give a 3D internet. With disilver(I) octafluoroadipate [(CF2)n(COOAg)2, n=4], 2D porous sheets of [Ag2(dtpcp)2(C4F8(CO2)2)]·2mesitylene (3) are formed. In polymer 3 four dtpcp and two octafluoroadipates are linked together by silver(I) ions to give a cavity in which two guest mesitylene molecules are located. Coordination polymers of 2,11‐dithia[3.3]‐ paracyclopane (dtpcp) with in situ silver(I) perfluoro‐dicarboxylates characterized by single crystal X‐ray analysis are described. With disilver(I) tetrafluorosuccinate [(CF2)n‐ (COOAg)2, n=2], 1D chains of [Ag4(dtpcp)3‐ (C2F4(CO2)2)2]·2CH3OH (1) are given. Changing the silver salt to disilver(I) hexafluoroglutarate [(CF2)n(COOAg)2, n=3] produces a 3D structure with composition of [Ag2(dtpcp)(C3F6(CO2)2)] (2). With disilver(I) octafluoroadipate [(CF2)n(COOAg)2, n=4], 2D porous sheets with cavities, in which guest mesitylene molecules are located, are formed.