Diverse Intermolecular Interactions in Metal−Organic Frameworks Constructed with the New Supramolecular Synthon Ag<sub><i>n</i></sub>−L−Ag<sub><i>n</i></sub>(<i>n</i> = 4, 5) (H<sub>2</sub>L = 2,2′-Bis(prop-2-ynyloxy)biphenyl)

The three silver(I) coordination polymers [(Ag<sub>2</sub>L)(AgNO<sub>3</sub>)<sub>6</sub>(H<sub>2</sub>O)] (<b>1</b>), [(Ag<sub>2</sub>L)<sub>0.5</sub>(AgCF<sub>3</sub>CO<sub>2</sub>)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>2</b>), and [(Ag<sub>2</sub>L)(AgCF<sub>3</sub>CO<sub>2</sub>)<sub>7</sub>(CH<sub>3</sub>CN)<sub>3</sub>(μ<sub>2</sub>-H<sub>2</sub>O)] (<b>3</b>) have been constructed from the flexible multifunctional dianionic ligand L (H<sub>2</sub>L = 2,2′-bis(prop-2-ynyloxy)biphenyl), providing experimental evidence of coexisting uncommon intermolecular interactions (cation−π and π−π in <b>1</b>; cation−π and anion−π in <b>2</b>; CN···π and C−H···π in <b>3</b>) that stabilize their framework structures.