Development of Metal–Organic Nanotubes Exhibiting Low-Temperature, Reversible Exchange of Confined “Ice Channels”

Unruh, Daniel K.; Gojdas, Kyle; Libo, Anna; Forbes, Tori Z.

doi:10.1021/ja400303f

Cited by 100 publications

(157 citation statements)

References 29 publications

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“…19,21 Racemic co-crystals of tubular cages DFT dimer calculations were performed to establish whether chiral recognition between cages might induce heterochiral window-to-window packing and hence the formation of isostructural nanotubes (Supplementary Information, Section 4.2, Supplementary Table 7). Using TCC2 as a test case, the heterochiral TCC2-R/TCC2-S pair was found to be favoured over the corresponding homochiral TCC2-R pair (-130 and -104 kJ mol -1 respectively), mirroring the heterochiral pairing preference for tetrahedral CC3 22,23 (Fig. 1f).…”

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confidence: 84%

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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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confidence: 84%

“…1f), but 1-D pore channels are also attractive. For example, 1-D pores have been used to study water transport 23,24 and the host-guest chemistry of linear molecules. 25 1-D porous structures were also used as templates for 1-D nanowires 26 and as efficient molecular sieves.…”

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confidence: 99%

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

et al. 2016

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“…This is in stark contrast to the water molecules present in the UIDA compounds, where there are limited interactions between the confined water molecules and the interior walls of the nanotube, but strong H-bonding networks between water molecules to form an ice-like conformation ( Figure S5, Supporting Information). 31 Single-crystal X-ray diffraction experiments on the UPDC compound suggested variations in hydration state and the identity of the ligated solvent molecule on the uranyl polyhedra. The interstitial water molecule was located again in the structural characterization of a different UPDC crystal, and the occupancy was allowed to free refine to a factor of 0.2014, indicating there may be some variability to the hydration state of the material.…”

Section: Crystal Growth and Designmentioning

confidence: 99%

“…Previous thermochemical characterization of the material has determined that there are limited interactions between the confined water molecules and the interior walls of the nanotube. 51 Initial uptake investigations utilizing hexane and DMSO to represent nonpolar and polar solvents found no evidence of uptake into the material, 31 suggesting that the compound exhibits selectivity to water, but the mechanism for this selectivity is poorly understood.…”

Section: ■ Introductionmentioning

confidence: 99%

Structural Features in Metal–Organic Nanotube Crystals That Influence Stability and Solvent Uptake

Jayasinghe

Unruh

Kral

et al. 2015

Crystal Growth & Design

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Porous hybrid materials such as metal−organic nanotubes are of interest due to synthetic tunability, possibility for 1-D flow, and confinement of solvent molecules. In the current study, the stability and solvent selectivity of two hybrid materials with nanotubular arrays, (pip) 0.5 [(UO 2 )(HIDA)(H 2 IDA)]·2H 2 O (UIDA; IDA = iminodiacetate) and [(UO 2 )(PDC)(H 2 O)] (UPDC; PDC = pyridine dicarboxylate) were analyzed using X-ray diffraction, gas chromatography/ mass spectrometry, thermogravimetric analysis, and infrared spectroscopy. The fine details of the structural characterization, such as the presence of solvent molecules, were found to be important to the overall properties of the materials as evidenced by the increased stability of the UIDA compound when formed from a solvent mixture containing acetone. Careful analysis of the UPDC compound indicated that the ligated solvent molecule can be exchanged, which may impact the hydration state of the material. Overall, the UIDA compound displays complete selectivity to water, but the UPDC compound adsorbs THF, methanol, ethanol, and cyclohexane.

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“…In contrast, framework structures are less common for uranyl oxysalts [6], and the current knowledge concerning purely inorganic nanotubules is limited to three uranyl selenate based species [7,8,9], which differ in their inner diameters, viz., two of them are 0.7 nm [7,8] and the other one is 1.5 nm [9]. In other, not purely inorganic, U(VI) compounds, such as metal–organic or hybrid systems, the number of structures containing nanotubules is higher [10,11,12]. …”

Section: Introductionmentioning

confidence: 99%

Uranyl Sulfate Nanotubules Templated by N-phenylglycine

et al. 2018

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The synthesis, structure, and infrared spectroscopy properties of the new organically templated uranyl sulfate Na(phgH+)7[(UO2)6(SO4)10](H2O)3.5 (1), obtained at room temperature by evaporation from aqueous solution, are reported. Its structure contains unique uranyl sulfate [(UO2)6(SO4)10]8− nanotubules templated by protonated N-phenylglycine (C6H5NH2CH2COOH)+. Their internal diameter is 1.4 nm. Each of the nanotubules is built from uranyl sulfate rings sharing common SO4 tetrahedra. The template plays an important role in the formation of the complex structure of 1. The aromatic rings are stacked parallel to each other due to the effect of π–π interaction with their side chains extending into the gaps between the nanotubules.

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Development of Metal–Organic Nanotubes Exhibiting Low-Temperature, Reversible Exchange of Confined “Ice Channels”

Cited by 100 publications

References 29 publications

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

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

Structural Features in Metal–Organic Nanotube Crystals That Influence Stability and Solvent Uptake

Uranyl Sulfate Nanotubules Templated by N-phenylglycine

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