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Synthesis and Crystal Structure of Ag4Br4 Nanoclusters in the Sodalite Cavities of Fully K+-Exchanged Zeolite A (LTA)
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  • Synthesis and Crystal Structure of Ag4Br4 Nanoclusters in the Sodalite Cavities of Fully K+-Exchanged Zeolite A (LTA)
저자명
Lim. Woo-Taik,Choi. Sik-Young,Kim. Bok-Jo,Kim. Chang-Min,Lee. In-Su,Kim. Seok-Han,Heo. Nam-Ho
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2005년|26권 7호|pp.1090-1096 (7 pages)
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

$Ag_4Br_4$ nanoclusters have been synthesized in about 75% of the sodalite cavities of fully $K^+$-exchanged zeolite A (LTA). An additional KBr molecule is retained in each large cavity as part of a near square-planar $K_4Br^{3+}$ cation. A single crystal of $Ag_{12}$-A, prepared by the dynamic ion-exchange of $Na_{12}$-A with aqueous 0.05 M $AgNO_3$ and washed with $CH_3OH$, was placed in a stream of flowing 0.05 M KBr in $CH_3OH$ for two days. The crystal structure of the product ($K_9(K_4Br)Si_{12}Al_{12}O_{48}{cdot}0.75Ag_4Br_4$, a = 12.186(1) $AA$) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm m. It was refined with all measured reflections to the final error index $R_1$ = 0.080 for the 99 reflections for which $F_o;{gt};4_{sigma};(F_o)$. The thirteen $K^+$ ions per unit cell are found at three crystallographically distinct positions: eight $K^+$ ions in the large cavity fill the six-ring site, three $K^+$ ions fill the eight-rings, and two $K^+$ ions are opposite four-rings in the large cavity. One bromide ion per unit cell lies opposite a four-ring in the large cavity, held there by two eight-ring and two six-ring $K^+$ ions ($K_4Br^{3+}$). Three $Ag^+$ and three $Br^-$ions per unit cell are found on 3-fold axes in the sodalite unit, indicating the formation of nano-sized $Ag_4Br_4$ clusters (interpenetrating tetrahedra; symmetry $T_d$; diameter ca. 7.9 $AA$) in 75% of the sodalite units. Each cluster (Ag-Br = 2.93(3) $AA$) is held in place by the coordination of its four $Ag^+$ ions to the zeolite framework (each $Ag^+$ cation is 2.52(3) $AA$ from three six-ring oxygens) and by the coordination of its four $Br^-$ ions to $K^+$ ions through six-rings (Br-K = 3.00(4) $AA$).