• Title/Summary/Keyword: Anionic framework

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A Novel 3D Polypseudo-rotaxane Metal-organic Framework Based on a Flexible Bis-pyridyl-bis-amide Ligand

  • Wang, Xiu-Li;Han, Na;Lin, Hong-Yan;Xu, Chuang;Luan, Jian;Liu, Guo-Cheng
    • Bulletin of the Korean Chemical Society
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    • v.33 no.11
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    • pp.3793-3796
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    • 2012
  • A novel 3D compound $\{[Cu(L)(H_2O)_4][Cu_2(SIP)_2(L)_2]\}{\cdot}2H_2O$ (1) (L = N,N-bis(4-pyridinecarboxamide)-1,4-butane, SIP = 5-sulfoisophthalate) is hydrothermally synthesized. X-ray diffraction analysis reveals that compound 1 is composed of 2D anionic $[Cu_2(SIP)_2(L)_2]_n{^{2n-}}$ double-layers and discrete 1D cationic $[CuL(H_2O)_4]_n{^{2n+}}$ polymeric chains, which represents a rare 3D polypseudo-rotaxane MOF from intercalation of 1D and 2D framework. In addition, the luminescent property and electrochemical behavior of compound 1 have been investigated.

Weak Interactions Between Organic Molecules and Alkali Metal Ions Present in Zeolites Help Manipulate the Excited State Behavior of Organic Molecules

  • Ramamurthy, V.
    • Journal of Photoscience
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    • v.10 no.1
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    • pp.127-148
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    • 2003
  • Zeolite is a porous highly interactive matrix. Zeolitic cations help to generate triplets from molecules that possess poor intersystem crossing efficiency. Certain zeolites act as electron acceptors and thus can spontaneously generate radical cations. Zeolites also act as proton donors and thus yield carbocations without any additional reagents. These reactive species, radical cations and carbocations, have long lifetime within a zeolite and thus lend themselves to be handled as ‘regular’ chemicals. Internal structure of zeolites is studded with cations, the counter-ions of the anionic framework. The internal constrained structure and the cations serve as handles for chemists to control the behavior of guest molecules included within zeolites.

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Two Crystal Structures of Dehydrated Fully $Ca^{2+}$-Exchanged Zeolte A Reacting with Rubidium Vapor

  • Song, Seong-Hwan;Kim, Yang
    • Bulletin of the Korean Chemical Society
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    • v.14 no.2
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    • pp.258-262
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    • 1993
  • Two single crystals of fully dehydrated $Rb^+$ -exchanged zeolite A have been prepared by the reduction of all $Ca^{2+}$ ions in dehydrated $Ca_6$-A by rubidium vapor. Their structures were determined by single crystal X-ray diffraction methods in the cubic space group Pm3m (a=12.160(2) $^{\AA}$ and 12.166(2) $^{\AA}$) at 22(1)$^{\circ}$C. In these structures, 12.4(2) to 13.3(2) Rb species are found per unit cell, more than 12 Rb$^+$ ions needed to balance the anionic charge of the zeolite framework, indicating that the sorption $Rb^0$ has occurred. In each structure, three $Rb^+$ ions per unit cell are located at the centers of the 8-rings. Six to eight $Rb^+$ ions are found opposite the 6-rings on threefold axes, and three $Rb^+$ ions are found in a sodalite unit. About 0.5 $Rb^+$ ion lies opposite a 4-ring. The structural analysis indicates the presence of a triangular rubidium cluster in the sodalite cavities. The triangular rubidium clusters may be stabilized by the coordination to two and/or three rubidium ions in the large cavity. Therefore, this cluster may be viewed as $(Rb_5)^{4+}$ and/or $(Rb_6)^{4+}$.

Sorption of Arsenate by the Calcined Mg-Al Layered Double Hydroxide (소성된 Mg-Al Layered Double Hydroxide에 의한 비소(V)의 흡착)

  • Seo, Young-Jin;Kang, Yun-Ju;Choi, Jung;Kim, Jun-Hyeong;Park, Man
    • Korean Journal of Soil Science and Fertilizer
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    • v.41 no.6
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    • pp.369-373
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    • 2008
  • Special concern has been given to the elevated arsenic content in soils because of its high mobility and toxicity. Layered double hydroxide (LDH) which has a high anionic exchange capacity is another potential anion adsorbent for toxic anions such as arsenic, chromate and selenium etc. The uptake of arsenate from aqueous solutions by the calcined Mg-Al LDH has been investigated. The sorption capacity was about 530 mmol/kg. Sorption isotherm was defined as L-type in which arsenate was removed by LDH through anion uptake reaction. Arsenate sorption by the calcined Mg-Al LDH was occurred by reconstruction of LDH's framework. Competitive adsorption revealed that Mg-Al LDH had higher selectivity for arsenate than for sulfate. These results strongly suggest that calcined Mg-Al LDH has a promising potential for efficient removal of toxic metal oxides like arsenates from aqueous environments.

Crystallographic Study on Zeolite 4A Reacted with Rubidium Vapor (루비듐 증기와 반응한 제올라이트 4A에 대한 결정학적 연구)

  • Song, Seong-Hwan;Kim, Yang;Han, Young-Wook
    • Journal of the Mineralogical Society of Korea
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    • v.4 no.2
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    • pp.99-107
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    • 1991
  • Three fully dehydrated fully Rb+-exchanged zeolite A single crystals have been prepared by the reduction of all Na+ ions in dehydrated Na12-A by rubidium vapor at various experimental conditions (220 $\leq$ T $\leq$ 33$0^{\circ}C$, 2 $\leq$ t $\leq$24 hours, and 0.1 $\leq$ PRb $\leq$ 1.1 Torr). Their structures were determined by single-crystal X-ray diffraction methods in the space group {{{{ RHO }}m3m (a=12.245(3) A) at 22(1)$^{\circ}C$. In these structures 12.6(2) to 13.5(2) Rb species are found per unit cell, more than the 12 Rb+ ions needed to balance the anionic charge of the zeolite framework, indication that the sorption of Rb0 has occurred. In each structure, three Rb+ ions per unit cell are located at the centers of 8-rings. Beyond that, the fractional occupancies observed are simply explained by two unit cell arrangments. In one, two Rb+ ions are in the sodalite unit near opposite 6-rings, six are in the large cavity near 6-ring, and one is in the large cavity near a 4-ring. In the other, three Rb species in the sodalite cavity (forming a triangle 3.7 A on an edge) each bond (3.4 A) through a 6-ring to an Rb species in the large cavity to give an (Rb6)4+ cluster of symmetry 3m (C3V). Five additional Rb+ ions fill the remaining large-cavity 6-ring sites.

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Crystal Structures of Zeolite X Exchanged by Two Different Cations. Structures of Cd32Cs28-X and Cd28Rb36-X (X=Si100Al92O384)

  • Jeong, Gyoung-Hwa;Kim, Yang
    • Bulletin of the Korean Chemical Society
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    • v.23 no.8
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    • pp.1121-1126
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    • 2002
  • Two anhydrous crystal structures of fully dehydrated Cd2+ - and Cs+ -exchanged zeolite X, Cd32Cs28Si100Al92O384 (Cd32Cs28-X: a = 24.828(11) $\AA)$ and fully dehydrated Cd,sup>2+ - and Rb+ -exchanged zeolite X, Cd28Rb36Si100Al92O384 (Cd28Rb36-X: a = 24.794(2) $\AA$), have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ The structures were refined to the final error indices, R1 = 0.058 and R2 = 0.065 with 637 reflections for Cd32Cs28-X and R1 = 0.086 and R2 = 0.113 with 521 reflections for Cd28Rb36-X for which I > $3\sigma(I)$. In the structure of Cd,sub>32Cs28-X, 16 Cd2+ ions fill the octahedral sites I at the centers of the double six rings (Cd-O = $2.358(8)\AA$ and O-Cd-O = $90.8(3)^{\circ}$ ). The remaining 16 Cd2+ ions occupy site II (Cd-O = $2.194(8)\AA$ and O-Cd-O = $119.7(4)^{\circ})$ and six Cs+ ions occupy site II opposite to the single six-rings in the supercage; each is $2.322\AA$ from the plane of three oxygens (Cs-O = 3.193(13) and O-Cs-O = $73.0(2)^{\circ}).$ Aboutten Cs+ ions are found at site II', $1.974\AA$ into the sodalite cavity from their three oxygen plane (Cs-O = $2.947(8)\AA$ and O-Cs-O = $80.2(3)^{\circ}).$ The remaining 12 Cs+ ions are distributed over site III' (Cs-O = 3.143(9) and O-Cs-O= $59.1(2)^{\circ})$. In the structure of Cd28Rb36-X, 16 Cd2+ ions fill the octahedral sites I at the center of the double-sixrings (Cd-O = 2.349(15) and O-Cd-O = $91.3(5)^{\circ}$ ). Another 12 Cd2+ ions occupy two different II sites (Cd-O = $2.171(18)/2.269(17)\AA$ and O-Cd-O = $119.7(7)/113.2(7)^{\circ}).$ Fifteen Rb+ ions occupy site II (Rb-O = $2.707(17)\AA$ and O-Rb-O = $87.8(5)^{\circ}).$ The remaining 21 Rb+ ions are distributed over site III' (Rb-O = $3.001(16)\AA$ and O-Rb-O = $60.7(4)^{\circ})$. It appears that the smaller and more highly charged Cd2+ ions prefer sites I and Ⅱ in that order, and the larger Rb+ and Cs+ ions, which are less able to balance the anionic charge of the zeolite framework, occupy sites II and II' with the remainder going to the least suitable site in the structure, site III'.The maximum Cs+ and Rb+ ion exchanges were 30% and 39%, respectively. Because these cations are too largeto enter the small cavities and their charge distributions may be unfavorable, cation-sieve effects might appear.

Crystal Structures of Fully Dehydrated Zeolite $Cd_6-A$ and of $Rb_{13.5}-A$, the Product of its Reaction with Rubidium, Containing Cationic Clusters

  • Jang, Se-Bok;Kim, Yang;Seff, Karl
    • Bulletin of the Korean Chemical Society
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    • v.15 no.3
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    • pp.236-241
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    • 1994
  • The crystal structures of $Cd_6-A$ evacuated at $2{\times}10^{-6}$ Torr and 750$^{\circ}$C (a=12.216(l) ${\AA}$), and of the product of its reaction with Rb vapor (a= 12.187(l) ${\AA}$), have been determined by single-crystal x-ray diffraction techniques in the cubic space group Pm$\bar{3}$m at 21(l)$^{\circ}$C. Their structures were refined to the final error indices, $R_1$=0.055 and $R_2$=0.067 with 191 reflections, and $R_1$=0.066 and $R_2$=0.049 with 90 reflections, respectively, for which I>3${\sigma}$(I). In dehydrated $Cd_6-A$, six $Cd^{2+}$ ions are found at two different threefold-axis sites near six-oxygen ring centers. Four $Cd^{2+}$ ions are recessed 0.50 ${\AA}$ into the sodalite cavity from the (111) plane at O(3), and the other two extend 0.28 ${\AA}$ into the large cavity from this plane. Treatment at 250 $^{\circ}$C with 0.1 Torr of Rb vapor reduces all $Cd^{2+}$ ions to give $Rb_{13.5^-}$A. Rb species are found at three crystallographic sites: three $Rb^+$ ions lie at eight-oxygen-ring centers, filling that position, and ca. 10.5 $Rb^+$ ions lie on threefold axes, 8.0 in the large cavity and 2.5 in the sodalite cavity. In this structure, ca. 1.5 Rb species more than the 12 $Rb^+$ ions needed to balance the anionic charge of zeolite framework are found, indicating that sorption of $Rb^0$ has occurred. The occupancies observed can be most simply explained by two "unit cell" compositions, $Rb_{12^-}A{\cdot}Rb$ and $Rb_{12^-}A{\cdot}2Rb$, of approximately equal population. In sodalite cavities, $Rb_{12^-}A{\cdot}Rb$ would have a $(Rb_2)^+$ cluster and $Rb_{12^-}A{\cdot}2Rb$ would have a triangular $(Rb_3)^+$ cluster. Each of the atoms of these clusters must bind further through a six-oxygen ring to a large cavity $Rb^+$ to give $(Rb_4)^{3+}$ (linear) and $(Rb_6)^{4+}$ (trigonal). Other unit-cell compositions and other cationic cluster compositions such as $(Rb_8)^{n+}$ may exist.

Three Crystal Structures of Dehydrated Partially $Co^{2+}-Exchanged$ Zeolite A Treated with Potassium Vapor (부분적으로 코발트 이온으로 치환한 제올라이트 A를 진공 탈수한 후 칼륨 증기로 반응시킨 3개의 결정구조)

  • Jeong Mi Suk;Jang Se Bok
    • Korean Journal of Crystallography
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    • v.15 no.2
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    • pp.59-68
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    • 2004
  • Three crystal structures of dehydrated partially $Co^{2+}-exchanged$ zeolite A treated with 0.6 Torr of K at $300^{\circ}C$ (for 12 hrs, 6 hrs, and 2 hrs) vapor have been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m at 21(1)$^{\circ}C(a=12.181(1)\;{\AA},\;a=12.184(1)\;{\AA},\;and\;a=12.215(1)\;{\AA})\;respectively)$. Their structures were refined to the final error indices, R(weight) of 0.090 with 10 reflections, 0.091 with 82 reflections, and 0.090 with 80 reflections, respectively, for which $1>\sigma(I)$. In each structure, all four $Co^{2+}$ and four $Na^+$ ions to be reduced by K atoms. The cobalt and sodium atoms produced are no longer found in the zeolite. K species are found at five different crystallographic sites: three $K^+$ ions lie at the planes of 8-rings, filling that position, ca. 11.5 K^+$ ions lie on threefold axes, ca. 4.0 in the large cavity and ca. 4.0 in the sodalite cavity, and ca. 0.5 $K^+$ ion is found near a 4-ring. ca. three $K^0$ atoms are found deep into the large cavity on threefold axes. In these structures, crystallographic results show that cationic tetrahedral $K_4$ (and/or triangular $K_3$) clusters have formed in the sodalites of zeolite A. The $K_4$ and/or $K_3$ clusters coordinate trigonally to three oxygens of a six-oxygen ring. The partially reduced ions of these clusters interact primarily with oxygen atoms of the zeolite structure rather than with each other. ca. 14.5K species are found per unit cell, more than the twelve $K^+$ ions needed to balance the anionic charge of zeolite framework, indicating that sorption of $K^0$ has occurred. The three $K^0$ atoms in the large cavity are closely associated with three out of four $K^+$ ions in the large cavity to form $K_7^{4+}$ clusters. The $K_7^{4+}$ cluster not interacts primarily with framework oxygens.

Crystal Structures of $Cd_6-A$ Dehydrated at $750^{\circ}C$ and Dehydrated $Cd_6-A$ Reacted with Cs Vapor ($750^{\circ}C$ 에서 탈수한 $Cd_6-A$의 결정구조와 이 결정을 세슘 증기로 반응시킨 결정구조)

  • Se Bok Jang;Yang Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.2
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    • pp.191-198
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    • 1993
  • The crystal structures of $Cd_{6-}A$ evacuated at $2{\times}10^{-6}$ torr and $750^{\circ}C$ (a = 12.204(1) $\AA$) and dehydrated $Cd_{6-}A$ reacted with 0.1 torr of Cs vapor at $250^{\circ}C$ for 12 hours (a = 12.279(1) $\AA$) have been determined by single crystal X-ray diffraction techniques in the cubic space group Pm3m at $21(1)^{\circ}C.$ Their structures were refined to final error indices, $R_1=$ 0.081 and $R_2=$ 0.091 with 151 reflections and $R_1=$ 0.095 and $R_2=$ 0.089 with 82 reflections, respectively, for which I > $3\sigma(I).$ In vacuum dehydrated $Cd_{6-}A$, six $Cd^{2+}$ ions occupy threefold-axis positions near 6-ring, recessed 0.460(3) $\AA$ into the sodalite cavity from the (111) plane at O(3) : Cd-O(3) = 2.18(2) $\AA$ and O(3)-Cd-O(3) = $115.7(4)^{\circ}.$ Upon treating it with 0.1 torr of Cs vapor at $250^{\circ}C$, all 6 $Cd^{2+}$ ions in dehydrated $Cd_{6-}A$ are reduced by Cs vapor and Cs species are found at 4 crystallographic sites : 3.0 $Cs^+$ ions lie at the centers of the 8-rings at sites of $D_{4h}$ symmetry; ca. 9.0 Cs+ ions lie on the threefold axes of unit cell, ca. 7 in the large cavity and ca. 2 in the sodalite cavity; ca. 0.5 $Cs^+$ ion is found near a 4-ring. In this structure, ca. 12.5 Cs species are found per unit cell, more than the twelve $Cs^+$ ions needed to balance the anionic charge of zeolite framework, indicating that sorption of Cs0 has occurred. The occupancies observed are simply explained by two unit cell arrangements, $Cs_{12}-A$ and $Cs_{13}-A$. About 50% of unit cells may have two $Cs^+$ ions in sodalite unit near opposite 6-rings, six in the large cavity near 6-ring and one in the large cavity near a 4-ring. The remaining 50% of unit cells may have two Cs species in the sodalite unit which are closely associated with two out of 8 $Cs^+$ ions in the large cavity to form linear $(Cs_4)^{3+}$ clusters. These clusters lie on threefold axes and extend through the centers of sodalite units. In all unit cells, three $Cs^+$ ions fill equipoints of symmetry $D_{4h}$ at the centers of 8-rings.

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