Isoreticular Homochiral Porous Metal−Organic Structures with Tunable Pore Sizes

Dybtsev, Danil N.; Yutkin, Maxim; Peresypkina, Eugenia V.; Вировец, А. В.; Serre, Christian; Férey, Gérard; Fedin, Vladimir P.

doi:10.1021/ic7009226

Cited by 151 publications

(62 citation statements)

References 29 publications

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“…[75,76,174,[205][206][207][208][209][210][211][212] However, despite their rich chemistry, catalysis with bio-MOFs is scarce. [213] This is often associated with stability and cost in MOF catalysis which is suitable for fine chemical synthesis rather than bulk chemistry.…”

Section: Catalysis and Separationsmentioning

confidence: 99%

Biologically derived metal organic frameworks

Anderson

Stylianou

2017

Coordination Chemistry Reviews

134

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Metal organic frameworks (MOFs) are extended structures composed of a network of organic ligands and metal ions or clusters connected to each other via coordination bonds. The numerous choices of organic ligands and metal coordination geometries have led to the construction of porous MOFs with various compositions, network topologies, pore sizes and shapes and they possess high surface areas and low densities. The structures of MOFs can be tailor-tuned in such a way that any desired ligand or/and metal ion can be incorporated; this has given to researchers the advantage of designing MOFs for a targeted application. Within this review, we overview recent examples of a sub-class of MOFs namely biologically derived MOFs (bio-MOFs), made of multifunctional and commercially available biologically derived ligands (bio-ligands) such as: amino acids, peptides, nucleobases and saccharides and focus on their coordination chemistry with a variety of metals. Central to this review are four tables detailing the coordination modes of bio-ligands to metals, along with a visual representation of the bio-MOF that is subsequently formed. Through the detail analysis of these structures, we highlight the structural impact of these ligands on the structure, and their contribution to the MOFs properties and applications. Finally, we showcase the potential of bio-MOFs in several research areas such as CO2 capture, separation, catalysis, drug delivery and sensing.

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Section: Catalysis and Separationsmentioning

confidence: 99%

Biologically derived metal organic frameworks

Anderson

Stylianou

2017

Coordination Chemistry Reviews

134

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“…A small size and a poor quality of crystals 1-3 did not allow their direct structural charac terization by X ray diffraction, however, the powder X ray diffraction data for 1-3 provided a conclusive evidence of their structural similarity to the zinc counter parts [Zn 2 (camph) 2 L]•G whose structure has been estab lished earlier, inter alia by single crystal X ray diffrac tion. 16 A comparison of X ray diffraction patterns for the copper(II) and zinc(II) complexes ( Fig. 1) shows that metal-organic frameworks of the copper and zinc cam phorates are structurally very similar.…”

Section: Resultsmentioning

confidence: 99%

Copper(II) camphorates with tunable pore size in metal-organic frameworks

2009

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Three new homochiral metal organic coordination polymers [Cu 2 camph 2 dabco]•DMF•2H 2 O, [Cu 2 camph 2 bipy]•3DMF•2H 2 O, and [Cu 2 camph 2 bpe]•4DMF•2H 2 O (H 2 camph is (+) cam phoric acid, bipy is 4,4′ bipyridyl, bpe is trans bis(4 pyridyl)ethylene) were synthesized by heating copper(II) nitrate, (+) camphoric acid, and N donor ligands of different length (dabco, bipy, bpe) in DMF and characterized by powder X ray diffraction, IR spectroscopy, and TGA. The obtained compounds are isostructural with the previously reported porous zinc(II) cam phorates.Porous metal organic coordination polymers belong to a new class of compounds whose inorganic and organic building blocks are arranged so that an organic ligand bridges the metal cations in a hybrid framework. 1-4 Tre mendous interest in these compounds is due to that they offer many ways of the functional design of coordination polymers and thus can be used to prepare new materias. 5,6 In particular, optically pure ligands give structures with the same configuration of chiral centers. Such coordina tion polymers are referred to as enantiomerically pure (homochiral). 7 Porous homochiral coordination polymers are regarded as promising materials for the separation or purification of enantiomers in complex mixtures 8-11 and for the enantioselective catalysis. 12-15 Of particular interest in this regard is the synthesis of diverse families of porous homochiral frameworks with changeable metal atoms and tunable pore size for the selective sorption/ activation of the molecules of only the desired size and configuration. Synthesis of porous homochiral coordina tion polymers poses challenges and is essentially restricted by the selection of the constituent organic ligands. The traditional approach exploits ligands, which are required to be chiral and simultaneously possess a sufficient length and steric rigidity to impart porosity and stability to the structure. 7 Organic compounds featuring all the above properties are often poorly available or are difficult to synthesize. Recently 8 we have proposed a strategy for the construction of porous homochiral coordination poly mers that allows the control of the structural parameters (pore size and the configuration of chiral centers) of the metal organic frameworks. The strategy is based on a com bination of two simple ligands: a small chiral multimodal ligand forming chiral complexes with the metal cations and a rigid bridging ligand assembling these complexes into a porous framework. One of the advantages of our method is the usage of relatively simple and available enantiomerically pure ligands. Following this strategy, we have for the first time prepared a range of homochiral frameworks 16 with the tunable pore size based on zinc(II), (+) camphoric acid (H 2 camph), and rigid bridging ligands of different length (dabco (diazabicyclo[2.2.2]octane), bipy (4,4´ bipyridyl), and bpe (trans bis(4 pyridyl) ethylene).Here we report synthesis and powder X ray diffraction study of three novel coordination polymers (copper(II)

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“…1). As a correspondingly inexpensive ligand source, D-camphoric acid, consisting of a rigid banding backbone based on a cyclopentane ring and two freely rotating carboxylate groups, has proved its effectiveness as a chiral building block for the syntheses of chiral MOFs materials with many transition metals [52][53][54]. It also can adopt a variety of coordination modes to participate in the formation of Ln cluster units due to the high affinity of lanthanide ions for oxygen donor atoms, resulting in diverse multidimensional structures.…”

Section: Synthesis Of Chiral Lanthanide Mofs With Chiral Ligandsmentioning

confidence: 99%

Chiral Lanthanide Metal-Organic Frameworks

Liu

Tang

2014

Structure and Bonding

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Chiral metal-organic frameworks (MOFs) have attracted much attention, not only due to their potential applications in enantioselective separation and catalysis, but also because of many advantages such as the high density of active catalytic centers, high level of porosity, regular and reliable crystalline nature, and relatively easy immobilization as compared to other heterogeneous systems. As metal-connecting nodes of MOFs, a large number of chemical synthetic strategies have focused on the transition metal ions which exhibit specific coordination geometries and restricted stereochemistry in the past two decades. However, the researches on chiral lanthanide MOFs are still limited up to now because of high coordination numbers, kinetic lability, weak stereochemical preference, and more variable nature of the coordination sphere for lanthanide ions. In this chapter, we would give a brief introduction to highlight the synthetic approaches reported and the structural features of chiral lanthanide MOFs or coordination polymer, which may be beneficial to explore structurally and functionally defined chiral solid materials.

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Isoreticular Homochiral Porous Metal−Organic Structures with Tunable Pore Sizes

Cited by 151 publications

References 29 publications

Biologically derived metal organic frameworks

Biologically derived metal organic frameworks

Copper(II) camphorates with tunable pore size in metal-organic frameworks

Chiral Lanthanide Metal-Organic Frameworks

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