Hierarchical Assembly of a Micro‐ and Macroporous Hydrogen‐Bonded Organic Framework with Tailored Single‐Crystal Size

Fernandez-Mato, Antonio; Halliwell, Christopher A.G.; Dann, Sandra E.; Ferrando‐Soria, Jesús; Plasser, Felix; Yendall, Keith A.; Ramos‐Fernández, Enrique V.; Vladisavljević, Goran T.; Elsegood, Mark R. J.

doi:10.1002/ange.202208677

Cited by 7 publications

(8 citation statements)

References 54 publications

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“…During the crystallization process and after thermal activation, the crystalline integrity of DFA-TPY is maintained, as con rmed by powder X-ray diffraction (PXRD) (Fig. S4) and matches with the phase of a recently reported microporous HOF [21]. The thermal stability of DFA-TPY building block was also studied by thermogravimetric analysis (TGA) under N 2 (Fig.…”

Section: Crystalline Assemblies With Double Hierarchical Architecture...supporting

confidence: 74%

“…The values in energy for both contributions, H-bonding and π-π stacking, accounts for 12 kcal/mol and 27 kcal/mol, respectively. The obtained energy value for the Hbond interaction on the co-crystals of Hybrid-1 for COOH … .N is higher than the H-bond value for N … .N in P2-TPY (12 kcal/mol vs 5.4 kcal/mol, respectively [21]), which would suggest that the driven mechanism of growth of Hybrid-1 on the surface of P2-TPY would be the stronger H-bond interactions originated at the interface between TPY and 3COOH crystals. The thermal stability of P2-TPY@Hybrid-1 building block was also studied by thermogravimetric analysis (TGA) under N 2 (Fig.…”

Section: Crystalline Assemblies With Hierarchical Architecturescompos...mentioning

confidence: 58%

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A simple and sequential strategy for the introduction of complexity and hierarchy in hydrogen-bonded organic (HOFs) crystals for environmental applications

Fernández,

Halliwell,

Jolley

et al. 2024

Preprint

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Hydrogen-bonded organic frameworks (HOFs) are a new class of crystalline porous organic molecular materials (POMMs) with great potential for a diverse range of applications. HOFs face common challenges to POMMs, and in general to purely organic crystals, that is, the difficulty of integrating multiple hierarchies in crystals. Herein, we proposed a simple and sequential strategy for the formation of hierarchical HOFs, including combined hierarchies in composition, architecture, and porosity. The strategy is based on controlling the assembly conditions, avoiding the use of any surface functionalization or template and obtaining hierarchical crystalline porous structures in an easy manner. As proof of concept, we demonstrate that hierarchical HOF crystals can be used to assemble crystals with superhydrophobicity and trapping abilities for the capture of persistent water contaminants such as oils and microplastics. We expect that this strategy could serve as inspiration for the construction of more intricated multiscale structures that could greatly expand the library of HOFs materials.

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Section: Crystalline Assemblies With Double Hierarchical Architecture...supporting

confidence: 74%

Section: Crystalline Assemblies With Hierarchical Architecturescompos...mentioning

confidence: 58%

A simple and sequential strategy for the introduction of complexity and hierarchy in hydrogen-bonded organic (HOFs) crystals for environmental applications

Fernández,

Halliwell,

Jolley

et al. 2024

Preprint

Self Cite

View full text Add to dashboard Cite

show abstract

“…Hierarchical porosity describes a scenario where there are multiple pore sizes in the medium 34 forming a nested structure, like in a Russian matryoshka doll. 35 Such porosity can be found in geomaterials, extended framework materials, foams, fibres, vascular plants, or body tissues.…”

Section: Levels Of Connectivity: Spatial Variationsmentioning

confidence: 99%

“…) is assumed to be proportional to the difference in pore pressures. Equations ( 33)- (34) state that the external change in the amount of fluid in a pore set at any instant is balanced by the fluid flowing into the set whilst a certain amount of fluid is diffused inside the medium. It is required that 𝜕𝜁 (1,2) ∕𝜕𝑡 = −𝜕𝜁 (2,1) ∕𝜕𝑡 since the internal diffusion between the sets must be equal; fluid volume is assumed to be conserved and not compressed.…”

Section: Governing Equations Of Consolidationmentioning

confidence: 99%

Multi‐porous extension of anisotropic poroelasticity: Consolidation and related coefficients

Adamus,

Healy,

Meredith

et al. 2024

Num Anal Meth Geomechanics

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We propose the generalization of the anisotropic poroelasticity theory. At a large scale, a medium is viewed as quasi‐static, which is the original assumption of Biot. At a smaller scale, we distinguish different sets of pores or fractures that are characterized by various fluid pressures, which is the original poroelastic extension of Aifantis. In consequence, both instantaneous and time‐dependent deformation lead to fluid content variations that are different in each set. We present the equations for such phenomena, where the anisotropic properties of both the solid matrix and pore sets are assumed. Novel poroelastic coefficients that relate solid and fluid phases in our extension are proposed, and their physical meaning is determined. To demonstrate the utility of our equations and emphasize the meaning of new coefficients, we perform numerical simulations of a triple‐porosity consolidation. These simulations reveal positive pore pressure transients in the drained behaviour of weakly connected pore sets, and these may result in the mechanical weakening of the material.

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“…COFs generally form crystalline domains <1 μm, though recent advances have achieved crystallite sizes of ∼200 μm. , MOFs can achieve domains >100 μm when synthesized in the presence of coordinative modulators or when the coordination bonding is relatively weak . On the other hand, HOFs form through relatively weaker, more reversible noncovalent hydrogen bonds (2–10 kcal mol –1 ), allowing for greater defect correction and control over assembly to form larger crystallites (>1 cm) …”

Section: Introductionmentioning

confidence: 99%

Toward the Next Generation of Permanently Porous Materials: Halogen-Bonded Organic Frameworks

Moghadasnia,

Eckstein,

Martin

et al. 2024

Crystal Growth & Design

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Halogen bonding has emerged as a reliable and intuitive handle in crystal engineering, providing predictable, noncovalent interactions capable of directing supramolecular assembly into networks with varying degrees of dimensionality. Conceptually similar to hydrogen bonding, halogen bonding represents a virtually untapped space for realizing new low-density porous architectures with large, highly crystalline domains. With the foundational understanding gained from almost two decades of computational and empirical supramolecular investigations, we believe that halogen bonding is on the precipice of enabling a new class of noncovalently linked permanently porous materials, aptly called halogen-bonded organic frameworks (XOFs). This perspective focuses on defining the criteria for the classification of XOFs and highlights seminal works in both halogen and hydrogen bonding that play an integral role toward understanding the key strategies in both synthon and tecton design that will lead to assembly of materials with accessible void space and observable porosity. Finally, solvent activation procedures and desorption mechanisms are discussed toward the goal of achieving permanently porous frameworks and thrusting halogen bonding into the realm of porous materials.

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Hierarchical Assembly of a Micro‐ and Macroporous Hydrogen‐Bonded Organic Framework with Tailored Single‐Crystal Size

Abstract: Supporting information for this article is given via a link at the end of the document.

Cited by 7 publications

References 54 publications

A simple and sequential strategy for the introduction of complexity and hierarchy in hydrogen-bonded organic (HOFs) crystals for environmental applications

A simple and sequential strategy for the introduction of complexity and hierarchy in hydrogen-bonded organic (HOFs) crystals for environmental applications

Multi‐porous extension of anisotropic poroelasticity: Consolidation and related coefficients

Toward the Next Generation of Permanently Porous Materials: Halogen-Bonded Organic Frameworks

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