Notes 1564 Bull. Korean Chem. Soc. 2004, Vol. 25, No. 10 Notes 19 Å-Thick Sheet Consisting of Cages Shin A Kim, Young-A Lee, a Ki-Min Park, † Yoon-Bo Shim, and Ok-Sang Jung * Department of Chemistry and Center for Plastic Information System, Pusan National University, Pusan 609-735, Korea † Basic Science Institute, Gyungsang National University, Jinju 660-701, Korea Received May 24, 2004 Key Words : Silver I complex, Bis(4-pyridyl)diphenylsilane, Nano-thickness, Coordination polymers, Cage Interest in nanoporous materials stems from well-defined applications such as photoelectronic devices, ion exchangers, molecular sieves, sensors, biomimetics, catalysts, and arti- ficial storages. 1-5 Significant progress has been made in the tubular materials by self-assembly of metal halides with specifically designed building blocks, 6-8 even though seren- dipitous motifs have been sometimes constructed owing to the presence of unpredictable weak interactions. Among such building blocks, silicon-containing pyridyl ligands have been used as interesting spacers. 9-11 The exploitation of bis(4-pyridyl)diphenylsilane (L) has been hardly explored except for Pd II and Pt II rhomboids reported by Stang's group. 12 The spacer possesses a potential bidentate, a tetrahedral angle (N-Si-N, ~109 o ), an appropriate pyridyl length, conformational nonrigidity, and bulkiness. In partic- ular, silver(I) ion has been employed as various directional units such as linear, tetrahedral, or T-shape. 13 We report a unique 19 Å-thick network consisting of cages along with its physicochemical properties. Experimental Section Materials and Measurements. AgClO 4 and NaX (X − = PF 6 − , NO 3 − ) were purchased from Aldrich and Junsei Chemical Co., respectively, and were used without further purification. The ligand L was prepared by the literature procedure. 12 Elemental microanalyses (C, H, N) were performed on crystalline samples by the Advanced Analysis Center at KIST using a Perkin Elmer 2400 CHN analyzer. Thermal analyses were carried out under a dinitrogen atmosphere at a scan rate of 10 o C/min using a Stanton Red Croft TG 100. Infrared spectra were obtained on a Perkin Elmer 16F PC FTIR spectrophotometer with samples prepared as KBr pellets. Preparation of [Ag I L 2 ](ClO 4 ). A methanol solution (15 mL) of L (85 mg, 0.25 mmol) was slowly diffused into an aqueous solution (15 mL) of AgClO 4 ·H 2 O (28 mg, 0.12 mmol). Colorless crystals of [Ag I L 2 ](ClO 4 ) formed at the interface, and were obtained in 3 days in 80% yield. mp. 110 ºC (dec). IR (KBr, cm −1 ): ν (ClO 4 ), 1120 (s). Anal. found: C, 59.40; H, 4.17; N, 6.36. Calcd for C 44 H 36 N 4 O 4 ClSi 2 Ag: C, 59.76; H, 4.10; N, 6.34. X-ray Crystallography. All X-ray data were collected on a Bruker SMART automatic diffractometer with a graphite- monochromated MoKα radiation (λ = 0.71073 Å) and a CCD detector at ambient temperature. The 45 frames of two dimensional diffraction images were collected and processed to obtain the cell parameters and orientation matrix. The data were corrected for Lorentz and polarization effects. The structures were solved by the Patterson method (SHELXS 97) and refined by full-matrix least square techniques (SHELXL 97). 14 The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were placed in calculated * Corresponding Author. Tel.: +82-51-510-2591; Fax: +82-51-516- 7421, e-mail: oksjung@pusan.ac.kr a Present address: Department of Chemistry, Chonbuk National Univer- sity, Jeonju 561-756, Korea Table 1. Crystallographic Data for [Ag I L2](ClO4) formula C44H36N4O4ClSi2Ag f.w. 884.27 space group C2/c a, Å 9.529(1) b, Å 18.928(2) c, Å 23.969(3) V , Å 3 4260.6(8) Z 4 dcal, gcm −3 1.379 µ, mm −1 0.638 Crystal size (mm 3 ) 0.05 × 0.2 × 0.3 Completeness to theta = 27.46 98.1% Data/restraints/parameters 5181 / 0 / 254 R {I > 2 σ(I)} R1 = 0.0617 wR2 = 0.1090 R1 = Σ||Fo|-|Fc||/Σ|Fo|. wR2 = Σw(Fo 2 -Fc 2 ) 2 /ΣwFo 4 ) 1/2