Cyclotetrabenzoin: Facile Synthesis of a Shape‐Persistent Molecular Square and Its Assembly into Hydrogen‐Bonded Nanotubes

Ji, Qing; Le, Ha T. M.; Wang, Xiqu; Chen, Yu‐Sheng; Makarenko, Tatyana; Jacobson, Allan J.; Miljanić, Ognjen Š.

doi:10.1002/chem.201503851

Cited by 38 publications

(29 citation statements)

References 82 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Their low-density frameworks can be metastable or hydrolytically unstable, and an over-reliance on molecules having cooperative hydrogen-bonded motifs is synthetically constraining. Intrinsically porous molecules are rarely functionalized with directional hydrogen-bonding motifs, [6,8,[300][301][302] which presents the opportunity of a hybrid strategy. More generally, though, it is useful to also develop other design strategies to create porous molecular solids without resorting to or relying on hydrogen bonding.…”

Section: Modulating Crystal Packing In Porous Molecular Crystalsmentioning

confidence: 99%

The Chemistry of Porous Organic Molecular Materials

Little

Cooper

2020

Adv Funct Materials

277

189

View full text Add to dashboard Cite

Porous organic molecular materials are a subclass of porous solids that are defined by their modular, molecular structures, and the absence of extended covalent or coordination bonding in the solid-state. As a result, porous molecular materials are soluble and they can be processed into different forms, such as mixed matrix membranes. The structure of the porous modules can be fine-tuned for specific applications, such as gas isotope separations, and in some cases the solid-state properties of these materials can be defined by the structure of the porous molecule as viewed in isolation. In this review, the authors focus on the design of porous organic molecular materials and how their properties can be tuned for specific applications by using crystal engineering techniques. The authors distinguish between strategies where porosity is defined largely by the molecule itself, for example, in porous organic cages, and cases where porosity is generated by the solidstate crystalline assembly. They emphasize the importance of computational techniques in the de novo design of functional, porous organic molecular materials, and how molecular modeling is applied to understand the properties of these materials.

show abstract

Section: Modulating Crystal Packing In Porous Molecular Crystalsmentioning

confidence: 99%

The Chemistry of Porous Organic Molecular Materials

Little

Cooper

2020

Adv Funct Materials

277

189

View full text Add to dashboard Cite

show abstract

“…27 Molecular 1-D nanotubes, a subset of 1-D channel materials, have been reported previously, 30-34 but few are stable to guest removal to yield porous structures. 34,35 Also, molecular self-assembly approaches to form nanotubes have not been demonstrated across a range of different building blocks, as for isoreticular MOFs.Here, we translate our chiral recognition strategy (Fig. 1e,f) to produce 1-D supramolecular nanotubes.…”

mentioning

confidence: 99%

“…25 1-D porous structures were also used as templates for 1-D nanowires 26 and as efficient molecular sieves. 27 Molecular 1-D nanotubes, a subset of 1-D channel materials, have been reported previously, [30][31][32][33][34] but few are stable to guest removal to yield porous structures. 34,35 Also, molecular self-assembly approaches to form nanotubes have not been demonstrated across a range of different building blocks, as for isoreticular MOFs.…”

mentioning

confidence: 99%

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

et al. 2016

View full text Add to dashboard Cite

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 (...

show abstract

“…To do so, six molecules of 2 come together in a way that resembles functional self‐assembly of protein subunits; they position their ‐OH groups convergently, to create a highly hydrophilic cavity in the crystal. Reduced cyclotribenzoin crystallizes in a structure with small but functional pores, and our future work will be directed at exploring (1) the dynamics of encapsulated water clusters; (2) the possibility that other members of cyclobenzoin series could form analogously functional pores in the solid state; (3) the stabilization of other species within these pores; and (4) the existence of these hexamers of 2 in nonpolar solutions. Our results will be reported in due course.…”

Section: Methodsmentioning

confidence: 99%

Confinement of Water Pentamers within the Crystals of a Reduced Cyclotribenzoin

Alrayyani

Wang

Miljanić

2017

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Reduction of cyclotribenzoin with sodium borohydride produces a cone-shaped hexaol. Crystals of this hexaol, obtained from wet tetrahydrofuran, encapsulate clusters of five water molecules in an idealized hydrogen-bonded arrangement. The water pentamer is stabilized by hydrogen bonding with the -OH groups of the hexaol, and [O-H⋅⋅⋅π] interactions with the benzene rings of the reduced cyclotribenzoin.

show abstract

Cyclotetrabenzoin: Facile Synthesis of a Shape‐Persistent Molecular Square and Its Assembly into Hydrogen‐Bonded Nanotubes

Cited by 38 publications

References 82 publications

The Chemistry of Porous Organic Molecular Materials

The Chemistry of Porous Organic Molecular Materials

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

Confinement of Water Pentamers within the Crystals of a Reduced Cyclotribenzoin

Contact Info

Product

Resources

About