Mobility of silver(I) ions around the propeller ligand, hexaphenylbenzene (HPB), in silver(I) pi-complexes

This paper describes three novel and distinctive organosilver(I) complexes with propeller ligand, hexaphenylbenzene (HPB), whose structures are contro lled by selected solvents and anions. Treatment of HPB with AgClO4 and AgCF 3SO3 in toluene gave, complexes [Ag-4(HPB)(ClO4)(4)] 1 and [Ag-2(HPB)(CF3SO 3)(2)(toluene)] 2, respectively. The single-crystal X-ray analysis revealed that 1 contains 2-D sheet framework whereas 2 consists of l-D chain struct ure. In both complexes the anions play the role of linkers instead of space rs in the construction of polymeric structures. In contrast, complex [Ag-2( HPB)(ClO4)(2)(THF)(2)] 3, obtained by using tetrahydrofuran (THF) ill place of toluene in the synthetic process of 1, exhibits a discrete dimer. The f undamentals of the synthesis of these complexes, influences of anions and s olvents on their coordination networks, and physicochemical properties are discussed. The present findings may serve as a basis for understanding the construction of solid-state materials with designed architecture in crystal engineering. Crystallographic data are as follows. 1: C21H15Ag2Cl2O8, mono clinic, P2(1)/c, a = 10.543(2) Angstrom, b = 11.934(4) Angstrom, c = 16.224 (3) Angstrom, beta = 94.08(2)degrees, Z = 4. 2: C51H38-Ag2S2F6O6, monoclini c, C2/c, a = 18.200(4) Angstrom, b = 16.831(7) Angstrom, c = 16.244(3) Angs trom, beta = 110.96(2)degrees, Z = 8. 3: C25H23AgClO5, monoclinic, P2(1)/c, a = 11.321(3) Angstrom, b = 12.511(4) Angstrom, c = 16.357(3) Angstrom, be ta = 99.98(2)degrees, Z = 4.