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Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks
Morris, William,Volosskiy, Boris,Demir, Selcuk,Gá,ndara, Felipe,McGrier, Psaras L.,Furukawa, Hiroyasu,Cascio, Duilio,Stoddart, J. Fraser,Yaghi, Omar M. American Chemical Society 2012 Inorganic Chemistry Vol.51 No.12
<P>Three new metal–organic frameworks [MOF-525, Zr<SUB>6</SUB>O<SUB>4</SUB>(OH)<SUB>4</SUB>(TCPP-H<SUB>2</SUB>)<SUB>3</SUB>; MOF-535, Zr<SUB>6</SUB>O<SUB>4</SUB>(OH)<SUB>4</SUB>(XF)<SUB>3</SUB>; MOF-545, Zr<SUB>6</SUB>O<SUB>8</SUB>(H<SUB>2</SUB>O)<SUB>8</SUB>(TCPP-H<SUB>2</SUB>)<SUB>2</SUB>, where porphyrin H<SUB>4</SUB>-TCPP-H<SUB>2</SUB> = (C<SUB>48</SUB>H<SUB>24</SUB>O<SUB>8</SUB>N<SUB>4</SUB>) and cruciform H<SUB>4</SUB>-XF = (C<SUB>42</SUB>O<SUB>8</SUB>H<SUB>22</SUB>)] based on two new topologies, <B>ftw</B> and <B>csq</B>, have been synthesized and structurally characterized. MOF-525 and -535 are composed of Zr<SUB>6</SUB>O<SUB>4</SUB>(OH)<SUB>4</SUB> cuboctahedral units linked by either porphyrin (MOF-525) or cruciform (MOF-535). Another zirconium-containing unit, Zr<SUB>6</SUB>O<SUB>8</SUB>(H<SUB>2</SUB>O)<SUB>8</SUB>, is linked by porphyrin to give the MOF-545 structure. The structure of MOF-525 was obtained by analysis of powder X-ray diffraction data. The structures of MOF-535 and -545 were resolved from synchrotron single-crystal data. MOF-525, -535, and -545 have Brunauer–Emmett–Teller surface areas of 2620, 1120, and 2260 m<SUP>2</SUP>/g, respectively. In addition to their large surface areas, both porphyrin-containing MOFs are exceptionally chemically stable, maintaining their structures under aqueous and organic conditions. MOF-525 and -545 were metalated with iron(III) and copper(II) to yield the metalated analogues without losing their high surface area and chemical stability.</P><P>Within this paper, three new metal−organic frameworks are synthesized and structurally characterized, MOF-525, -535, and -545, based on two new topologies, <B>ftw</B> and <B>csq</B>. MOF-525 has the highest Brunauer−Emmett−Teller surface area and MOF-545 has the largest pores of any zirconium-based MOF, 2620 m<SUP>2</SUP>/g and 36 Å, respectively. Most importantly, MOF-525 and -545 contain porphyrin sites, which are metalated with copper(II) and iron(III).</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/inocaj/2012/inocaj.2012.51.issue-12/ic300825s/production/images/medium/ic-2012-00825s_0002.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic300825s'>ACS Electronic Supporting Info</A></P>
Nanoporous Carbohydrate Metal–Organic Frameworks
Forgan, Ross S.,Smaldone, Ronald A.,Gassensmith, Jeremiah J.,Furukawa, Hiroyasu,Cordes, David B.,Li, Qiaowei,Wilmer, Christopher E.,Botros, Youssry Y.,Snurr, Randall Q.,Slawin, Alexandra M. Z.,Stoddar American Chemical Society 2012 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.134 No.1
<P>The binding of alkali and alkaline earth metal cations by macrocyclic and diazamacrobicyclic polyethers, composed of ordered arrays of hard oxygen (and nitrogen) donor atoms, underpinned the development of host–guest supramolecular chemistry in the 1970s and 1980s. The arrangement of −OCCO– and −OCCN– chelating units in these preorganized receptors, including, but not limited to, crown ethers and cryptands, is responsible for the very high binding constants observed for their complexes with Group IA and IIA cations. The cyclodextrins (CDs), cyclic oligosaccharides derived microbiologically from starch, also display this −OCCO– bidentate motif on both their primary and secondary faces. The self-assembly, in aqueous alcohol, of infinite networks of extended structures, which have been termed CD-MOFs, wherein γ-cyclodextrin (γ-CD) is linked by coordination to Group IA and IIA metal cations to form metal–organic frameworks (MOFs), is reported. CD-MOF-1 and CD-MOF-2, prepared on the gram-scale from KOH and RbOH, respectively, form body-centered cubic arrangements of (γ-CD)<SUB>6</SUB> cubes linked by eight-coordinate alkali metal cations. These cubic CD-MOFs are (i) stable to the removal of solvents, (ii) permanently porous, with surface areas of ∼1200 m<SUP>2</SUP> g<SUP>–1</SUP>, and (iii) capable of storing gases and small molecules within their pores. The fact that the −OCCO– moieties of γ-CD are not prearranged in a manner conducive to encapsulating single metal cations has led to our isolating other infinite frameworks, with different topologies, from salts of Na<SUP>+</SUP>, Cs<SUP>+</SUP>, and Sr<SUP>2+</SUP>. This lack of preorganization is expressed emphatically in the case of Cs<SUP>+</SUP>, where two polymorphs assemble under identical conditions. CD-MOF-3 has the cubic topology observed for CD-MOFs 1 and 2, while CD-MOF-4 displays a channel structure wherein γ-CD tori are perfectly stacked in one dimension in a manner reminiscent of the structures of some γ-CD solvates, but with added crystal stability imparted by metal–ion coordination. These new MOFs demonstrate that the CDs can indeed function as ligands for alkali and alkaline earth metal cations in a manner similar to that found with crown ethers. These inexpensive, green, nanoporous materials exhibit absorption properties which make them realistic candidates for commercial development, not least of all because edible derivatives, fit for human consumption, can be prepared entirely from food-grade ingredients.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2012/jacsat.2012.134.issue-1/ja208224f/production/images/medium/ja-2011-08224f_0007.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja208224f'>ACS Electronic Supporting Info</A></P>
Large-Pore Apertures in a Series of Metal-Organic Frameworks
Deng, H.,Grunder, S.,Cordova, K. E.,Valente, C.,Furukawa, H.,Hmadeh, M.,Gandara, F.,Whalley, A. C.,Liu, Z.,Asahina, S.,Kazumori, H.,O'Keeffe, M.,Terasaki, O.,Stoddart, J. F.,Yaghi, O. M. American Association for the Advancement of Scienc 2012 Science Vol.336 No.6084
<P>We report a strategy to expand the pore aperture of metal-organic frameworks (MOFs) into a previously unattained size regime (>32 angstroms). Specifically, the systematic expansion of a well-known MOF structure, MOF-74, from its original link of one phenylene ring (I) to two, three, four, five, six, seven, nine, and eleven (II to XI, respectively), afforded an isoreticular series of MOF-74 structures (termed IRMOF-74-I to XI) with pore apertures ranging from 14 to 98 angstroms. All members of this series have noninterpenetrating structures and exhibit robust architectures, as evidenced by their permanent porosity and high thermal stability (up to 300C). The pore apertures of an oligoethylene glycol-functionalized IRMOF-74-VII and IRMOF-74-IX are large enough for natural proteins to enter the pores.</P>
Furukawa, Hiroyasu,Go, Yong Bok,Ko, Nakeun,Park, Young Kwan,Uribe-Romo, Fernando J.,Kim, Jaheon,O’Keeffe, Michael,Yaghi, Omar M. American Chemical Society 2011 Inorganic Chemistry Vol.50 No.18
<P>The concept and occurrence of isoreticular (same topology) series of metal–organic frameworks (MOFs) is reviewed. We describe the preparation, characterization, and crystal structures of three new MOFs that are isoreticular expansions of known materials with the <B>tbo</B> (Cu<SUB>3</SUB>(4,4′,4″-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tribenzoate)<SUB>2</SUB>, MOF-399) and <B>pto</B> topologies (Cu<SUB>3</SUB>(4,4′,4″-(benzene-1,3,5-triyl-tribenzoate)<SUB>2</SUB>, MOF-143; Cu<SUB>3</SUB>(4,4′,4″-(triazine-2,4,6-triyl-tris(benzene-4,1-diyl))tribenzoate)<SUB>2</SUB>, MOF-388). One of these materials (MOF-399) has a unit cell volume 17 times larger than that of the first reported material isoreticular to it, and has the highest porosity (94%) and lowest density (0.126 g cm<SUP>–3</SUP>) of any MOFs reported to date.</P><P>Syntheses of three new metal−organic frameworks (MOFs) that are isoreticular (same topology) expansions of known materials with the <B>tbo</B> and <B>pto</B> topologies are reported. One of these materials (MOF-399) has a unit cell volume 17 times larger than that of the first reported material isoreticular to it, and has the highest void fraction (94%) and lowest density (0.126 g cm<SUP>−3</SUP>) of any MOFs reported to date.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/inocaj/2011/inocaj.2011.50.issue-18/ic201376t/production/images/medium/ic-2011-01376t_0007.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic201376t'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic201376t'>ACS Electronic Supporting Info</A></P>
Furukawa, Y.,Matsukura, M.,Nakamura, O.,Miyamoto, A. The Korea Association of Crystal Growth 2008 韓國結晶成長學會誌 Vol.18 No.1
The growth of composite-structured Nd:$GdVO_4$ single crystal rods by the double die EFG method is reported. Two crucibles are combined with an outer and inner die for ascending of different melt. The composite-structured Nd:$GdVO_4$ single crystal rods with a length of 50 mm and an outer diameter of 5 mm including of inner Nd-doped core region with diameter 3 mm were grown successfully. Nd distribution in the, radial direction has graded profile from result of EPMA. Absorption coefficient in the core region at 808 nm was $42cm^{-1}$. Finally, we demonstrated the laser oscillation using our composite crystal and 2-W output was obtained.