Mobility of Silver(I) Ions around the Propeller Ligand, Hexaphenylbenzene (HPB), in Silver(I) π-Complexes

This paper describes three novel and distinctive organosilver(I) complexes with propeller ligand, hexaphenylbenzene
(HPB), whose structures are controlled by selected solvents and anions. Treatment of HPB with AgClO4 and
AgCF3SO3 in toluene gave, complexes [Ag4(HPB)(ClO4)4] 1 and [Ag2(HPB)(CF3SO3)2(toluene)] 2, respectively.
The single-crystal X-ray analysis revealed that 1 contains 2-D sheet framework whereas 2 consists of 1-D chain
structure. In both complexes the anions play the role of linkers instead of spacers in the construction of polymeric
structures. In contrast, complex [Ag2(HPB)(ClO4)2(THF)2] 3, obtained by using tetrahydrofuran (THF) in place
of toluene in the synthetic process of 1, exhibits a discrete dimer. The fundamentals of the synthesis of these
complexes, influences of anions and solvents 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,
monoclinic, P21/c, a = 10.543(2) Å, b = 11.934(4) Å, c = 16.884(3) Å, β = 94.08(2)°, Z = 4. 2:  C51H38Ag2S2F6O6, monoclinic, C2/c, a = 18.200(4) Å, b = 16.831(7) Å, c = 16.244(3) Å, β = 110.96(2)°, Z = 8. 3: 
C25H23AgClO5, monoclinic, P21/c, a = 11.321(3) Å, b = 12.511(4) Å, c = 16.357(3) Å, β = 99.98(2)°, Z = 4.