Zeolitic Polyoxometalate-Based Metal−Organic Frameworks (Z-POMOFs): Computational Evaluation of Hypothetical Polymorphs and the Successful Targeted Synthesis of the Redox-Active Z-POMOF1

Rodríguez‐Albelo, L. Marleny; Ruiz‐Salvador, A. Rabdel; Sampieri, Álvaro; Lewis, Dewi W.; Gómez, Ariel; Nohra, Brigitte; Mialane, Pierre; Marrot, Jérôme; Sécheresse, Francis; Mellot‐Draznieks, Caroline; Biboum, Rosa Ngo; Keita, Bineta; Nadjo, L.; Dolbecq, Anne

doi:10.1021/ja905009e

Cited by 267 publications

(198 citation statements)

References 73 publications

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“…25) where the nanotubes are preserved, but where collapse of the cage occurs. The bulk TCC2-R/TCC2-S material was insufficiently crystalline to determine whether the loss of porosity was due to this cage collapse, to a loss of crystallinity, or to both.We also calculated the landscapes of possible crystal structures of enantiopure and racemic TCC1-TCC3 using crystal structure prediction (CSP) 21,39,40,41,42 methods (Fig. 5, Supplementary Information, Section 4.6).…”

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Reticular synthesis of porous molecular 1D nanotubes and 3D networks

et al. 2016

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Synthetic control over pore size and pore connectivity is the crowning achievement for porous metal-organic frameworks. The same level of control has not been achieved for molecular crystals, which are not defined by strong, directional intermolecular coordination bonds. Hence, molecular crystallization is inherently less controllable than framework crystallization, and there are fewer examples of 'reticular synthesis'-where multiple building blocks can be assembled according to a common assembly motif.Here, we apply a chiral recognition strategy to a new family of tubular covalent cages, to create both 1-D porous nanotubes and 3-D diamondoid pillared porous networks.The diamondoid networks are analogous to metal-organic frameworks prepared from tetrahedral metal nodes and linear, ditopic organic linkers. The crystal structures can be rationalized by computational lattice energy searches, which provide an in silico screening method to evaluate candidate molecular building blocks. These results are a blueprint for applying the 'node and strut' principles of reticular synthesis to molecular crystals.Despite many advances in supramolecular chemistry, it is still challenging to control molecular crystallization to create a specific, useful property. 1,2 This is important in the emerging area of porous molecular solids, 3 which have practical advantages such as solution processability. The crystal packing in porous molecular crystals defines the pore dimensions, which in turn define properties such as guest selectivity. 4,5 The same challenge-control over solid state structure-applies to all 2 functional molecular crystals because crystal packing defines physical properties such as electronic band gap and thermal or electrical conductivity.A central paradigm in crystal engineering is to synthesize building blocks, or 'tectons', with strong, directional interactions, such as hydrogen bonding 6 or metal-ligand binding, 7 which direct assembly into a targeted three-dimensional superstructure (Fig. 1). 1,2,8,9 For metal-organic frameworks (MOFs) and porous coordination polymers (PCPs), directional metal-ligand bonds are used to do this (Fig. 1a). [10][11][12][13][14] Likewise, hydrogen bonding can be used to create organic molecular crystals with defined network structures (Fig. 1b). 9,15,16 We have used chiral recognition to assemble porous organic cages 3 (POCs) into structures with 3-D pore channels (Fig. 1c). 3 POCs are rigid molecules with a permanent internal void that is accessible to guests via 'windows' in the cage. [17][18][19] Control of structure and function for POCs can be difficult, however, because slight changes in the molecular structure 19 or the crystallization solvent 20 can cause a profound change in the crystal packing. Chiral window-towindow interactions (Fig. 1e,f) can direct these POCs to assemble into 3-D pore networks in several cases, 19,21,22 but this is not ubiquitous. For example, some cages require specific solvents to template the window-to-window packing. 20 The chiral cage CC3-S (...

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“…We also calculated the landscapes of possible crystal structures of enantiopure and racemic TCC1-TCC3 using crystal structure prediction (CSP) 21,39,40,41,42 methods (Fig. 5, Supplementary Information, Section 4.6).…”

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Reticular synthesis of porous molecular 1D nanotubes and 3D networks

et al. 2016

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“…These studies have utilized a number of techniques to probe the mechanical properties of MOFs including nanoindentation, computation, and high-pressure crystallographic techniques. [1][2][3] Previous work includes highpressure crystallographic studies on the dense zeolitic imidazolate framework (ZIF) material Zn(Im) 2 (Im = imidazole), [4] the copper framework HKUST-1 ([Cu 3 (TMA) 2 (H 2 O) 3 ] n , [5] TMA = benzene-1,3,5-tricarboxylate) and ZIF-8 [Zn-(MeIM) 2 , MeIM = 2-methylimidazolate]. [6] In these studies GPa pressures were generated using a diamond anvil cell (DAC).…”

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The Effect of High Pressure on MOF‐5: Guest‐Induced Modification of Pore Size and Content at High Pressure

et al. 2011

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Grace under pressure: In the first high‐pressure crystallographic study on the metal–organic framework MOF‐5, increasing pressure initially results in the pressure‐transmitting fluid being squeezed into the pores. Further pressure increase causes a large reduction in pore content as solvent is evacuated from the pores, until a complete loss of crystallinity is observed at pressures above 3.2 GPa.

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“…[50][51][52][53][54][55][56][57][58][59][60][61][62] The terminal oxygen atoms or hydroxyl groups of POMs can be substituted by the oxygen atoms of carboxylates, while capping transition metals in some POM species can be chelated by organic ligands, leading to extended frameworks. [63][64][65][66][67] Although this approach can allow rational design of desired structures by assessing the geometries and the coordination numbers of the secondary building units (POM and linker) 46,68,69 it is often not the case, and materials may form serendipitously. 79 4 An alternative, third approach is to use hybrid POMs 70 that already have organic ligands grafted onto the inorganic cluster and that can be conceived and synthesised in a predefined geometry, with extended metal chelating units arranged in a similar manner to conventional, purely organic linkers.…”

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Synthetic Considerations in the Self-Assembly of Coordination Polymers of Pyridine-Functionalized Hybrid Mn-Anderson Polyoxometalates

Yazigi

Wilson

Long

et al. 2017

Crystal Growth & Design

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The incorporation of polyoxometalates (POMs) as structural units into ordered porous constructs such as metal-organic frameworks (MOFs) is desirable for a range of applications where intrinsic properties inherited from both the MOF and POM are utilised, including catalysis and magnetic data storage. The controlled self-assembly of targeted MOF topologies containing POM units is hampered by the wide range of oxo and hydroxo units on the peripheries of POMs that can act as coordinating groups towards linking metal cations leading to a diverse range of structures, but incorporation of organic donor units into hybrid POMs offers an alternative methodology to programmably synthesise POM/MOF conjugates. Herein, we report six coordination polymers obtained serendipitously wherein Zn 2+ and Cu 2+ link pyridine-appended Mn-Anderson clusters into two-and three-dimensional network solids with complex connectivities and topologies.2 Careful inspection of their solid-state structures has allowed us to identify common structuredirecting features across these coordination polymers, including a square motif where two Zn 2+ cations bridge two POMs. By correlating certain structural motifs with synthetic conditions we have formulated a series of design considerations for the self-assembly of coordination polymers of hybrid POMs, encompassing the selection of reaction conditions, co-ligands and linking metal cations. We anticipate that these synthetic guidelines will inform the future assembly of hybrid POMs into functional MOF materials. INTRODUCTIONPolyoxometalates ( ) that have been widely studied for their catalytic, [4][5][6][7][8][9] magnetic, 10-17 photochromic 18-21 and redox properties. [22][23][24][25][26][27][28] Given their large range of their chemical and physical properties, their incorporation into Metal-Organic Frameworks (MOFs) -network structures composed of metal clusters or metal ions connected by organic linkers -or more generally into porous frameworks has been investigated. 29,30 Creating POM/MOF conjugate materials can associate their individual properties, for instance the catalytic properties of a POM with the large surface area of a MOF, 31 or achieving a synergistic effect, for example the cooperative effect of single molecule magnets 32 or enhanced photocatalytic proton reduction. 33 To do so, two main approaches have been followed to date ( Figure 1a). The first is the impregnation of the POMs into the pores of a MOF, where POMs are either added during the MOF synthesis and trapped in the pores, [34][35][36][37][38][39][40] or they are inserted postsynthetically by soaking the MOF in a solution of the desired POM. [41][42][43][44] The second approach is to consider POMs as building blocks for porous structures, 45 with the aim of creating a bond between the POM and 3 either an organic linker (usually a multitopic carboxylic acid or N-donor ligand) [46][47][48][49] -di-(4-pyridyl)-1,4,5,8- (Figures 1b and 1c). The amido-pyridyl tris-alkoxo MnAnderson (POM-1) has been reported previously 76 and sh...

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Zeolitic Polyoxometalate-Based Metal−Organic Frameworks (Z-POMOFs): Computational Evaluation of Hypothetical Polymorphs and the Successful Targeted Synthesis of the Redox-Active Z-POMOF1

Cited by 267 publications

References 73 publications

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

The Effect of High Pressure on MOF‐5: Guest‐Induced Modification of Pore Size and Content at High Pressure

Synthetic Considerations in the Self-Assembly of Coordination Polymers of Pyridine-Functionalized Hybrid Mn-Anderson Polyoxometalates

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