- Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization
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Atomistic control of the coordination environment of lattice ions and the distribution of metal sites within crystalline mixed-metal coordination polymers remain significant synthetic challenges. Herein is reported the mechanochemical synthesis of a reticular family of crystalline heterobimetallic metal–organic frameworks (MOFs) is now achieved by polymerization of molecular Ru2[II,III] complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc)2. The resulting crystalline heterobimetallic MOFs are solid solutions of Ru2 and Cu2 sites housed within [M3L2] phases. The developed mechanochemical strategy is modular and allows for systematic control of the primary coordination sphere of the Ru2 sites within an isoreticular family of materials. This strategy is anticipated to provide a rational approach to atomically precise mixed-metal materials.
- Antonio, Alexandra M.,Bhuvanesh, Nattamai,Bloch, Eric D.,Ezazi, Andrew A.,Gao, Wen-Yang,Lorzing, Gregory R.,Powers, David C.,Sur, Aishanee,Taggart, Garrett A.,Wang, Chen-Hao
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- Hetero bi-paddle-wheel coordination networks: A new synthetic route to Rh-containing metal - Organic frameworks
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We have successfully synthesized rhodium-containing MOFs with 1:1 abundance ratios of paddle-wheel units of Rh2 and Cu2/Zn 2, i.e., [Rh2M2(1,4-bdc)2] ·nSolvent (M = Cu: RhCu-DMF, RhCu-EtOH; M = Zn: RhZn-DMF; 1,4- bdc: 1,4-benzenedicarboxylate) by a novel synthetic method involving assembly of discrete paddle-wheel dirhodium(II) tetra(1,4-benzenedicarboxylate) with Cu 2+ or Zn2+ ions. The diffraction patterns of these complexes were very similar to the predicted and experimental XRPD patterns reported for [Cu2(1,4-bdc)2]. This result indicates that this method enables the incorporation of coordinatively unsaturated noble-metal sites for the many reported MOFs with multi-carboxy ligands and paddle-wheel nodes.
- Matsunaga, Satoshi,Hasada, Ken-Ichi,Sugiura, Kenji,Kitamura, Naoki,Kudo, Yuri,Endo, Nanako,Mori, Wasuke
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- A novel method of complete activation by carbonyldiimidazole: application to ester synthesis
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The activation of carboxylic groups by carbonyldiimidazole (CDI) results in the presence of excess CDI; it is shown that this reacts rapidly with the target hydroxyl groups under acylation conditions, thus preventing the desired acylation even when an excess of reagent is present and resulting poor yields.The methods described result in rapid, complete, and convenient removal of the excess CDI.This procedure thus permits the use of sufficient excess of CDI to effect complete activation of the acid to the imidazole.The imidazolides prepared in this manner, when used in limiting amounts, can be quantitatively converted to esters or amides; when used in slight excess, these imidazolides result in the quantitative acylation of target groups.
- Morton, Robert C.,Mangroo, Dev,Gerber, Gerhard E.
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p. 1701 - 1705
(2007/10/02)
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