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

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posted on 19.11.1999, 00:00 by Gui Ling Ning, Megumu Munakata, Liang Ping Wu, Masahiko Maekawa, Yusaku Suenaga, Takayoshi Kuroda-Sowa, Kunihisa Sugimoto
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.