Switchable gate-opening effect in metal–organic polyhedra assemblies through solution processing

Craig, Gavin A.; Larpent, Patrick; Kusaka, Shinpei; Matsuda, Ryotaro; Kitagawa, Susumu; Furukawa, Shuhei

doi:10.1039/c8sc02263a

Cited by 41 publications

(57 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, similar step‐wise profiles are observed in the desorption process, suggesting that some kind of gating mechanism may be present for N 2 O but not for CO 2 due to the relative sizes of their dynamic radii. Similar gating process have been observed recently for a crystalline metal–organic cage …”

Section: Figuresupporting

confidence: 87%

A Multifunctional, Charge‐Neutral, Chiral Octahedral M₁₂L₁₂ Cage

Boer

White

Slater

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

A chiral, octahedral M12L12 cage, which is charge neutral and contains an internal void of about 2000 Å3, is reported. The cage was synthesised as an enantiopure complex by virtue of amino‐acid‐based dicarboxylate ligands, which assemble around copper paddlewheels at the vertices of the octahedron. The cage persists in solution with retention of the fluorescence properties of the parent acid. The solid‐state structure contains large pores both within and between the cages, and displays permanent porosity for the sorption of gases with retention of crystallinity. Initial tests show some enantioselectivity of the cage towards guests in solution.

show abstract

Section: Figuresupporting

confidence: 87%

A Multifunctional, Charge‐Neutral, Chiral Octahedral M₁₂L₁₂ Cage

Boer

White

Slater

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The quest for understanding specific host-guest-interactions in crystalline framework materials has significantly stimulated the rise of specifically adapted and parallelized characterization techniques (Fig. 5) [102][103][104][105][106] , as structural intermediates are only observable in situ, i.e., at a specific loading of the guest, by controlling the activity, temperature or external pressure. The analysis of elastic deformations and local interactions by inelastic neutron scattering 30,107 , NMR 13,108 , IR, and Raman spectroscopy 13 in the presence of guest molecules is well established 109,110 .…”

Section: Challenges and Advanced Methods For Analyzing A Framework-inmentioning

confidence: 99%

Four-dimensional metal-organic frameworks

et al. 2020

View full text Add to dashboard Cite

Recognising timescale as an adjustable dimension in porous solids provides a new perspective to develop novel four-dimensional framework materials. The deliberate design of three-dimensional porous framework architectures is a developed field; however, the understanding of dynamics in open frameworks leaves a number of key questions unanswered: What factors determine the spatiotemporal evolution of deformable networks? Can we deliberately engineer the response of dynamic materials along a time-axis? How can we engineer energy barriers for the selective recognition of molecules? Answering these questions will require significant methodological development to understand structural dynamics across a range of time and length scales. P orous framework materials offer outstanding functionality due to their wide range of tuneable building blocks and ultrahigh porosity 1-5. The integration of functions, such as chemisorptive, redox, optically or catalytically active centers, encapsulated drugs, enzymes, nanoparticles, and more, has led to the discovery of metal-organic framework (MOF) applications in gas separation, CO 2 sequestration, gas storage, catalysis, optics, and sensing, and a roadmap for integration into electronic systems has even been proposed 6-12. The chemistry of three-dimensional (3D) porous framework materials, connecting nodes and linkers through a variety of chemical bonds is enormously rich 13,14. While decades ago, rationalization was aided by topology analysis and isoreticular expansion 15,16 , in the age of digitalization computer-aided design plays a crucial role in predicting millions of new 3D structures and their properties 17-19. The serendipitous discovery of an adsorption induced structural transformation in a network nowadays termed ELM-11 20 stimulated researchers and laid the foundations for exploring novel dynamic phenomena in porous frameworks. Like enzymes, structural changes are stimulated by guest molecules intruding into the porous frameworks leading to macroscopic volume changes of up to 200-300%. The adaptive change of pore size is a fascinating feature, but a selectivity comparable to that of enzymes has not been reached yet. Emerging applications of adaptive porous materials Porosity switching in the crystalline solid state represents a unique phenomenon observed only in a limited number of porous materials 21-25. This flexibility was predicted in 1998 for MOFs by Kitagawa and coworkers, and later termed "3 rd Generation MOFs" 25-27. These materials are characterized by dynamic features of the framework structure and are also named "soft porous crystals" (SPCs). We briefly account here a few remarkable applications of the dynamic frameworks reported today as the premise for our following perspective (Fig. 1). In gas storage applications, the pore closing upon desorption provides almost ideal deliverable capacity, a key advantage compared with rigid adsorbents 28. More importantly, for gas separations, the selective response of the porous host in adapting the pore shape to a reco...

show abstract

“… 27 The raw data were reduced and corrected for Lorentz and polarization effects using CrystalClear 28 and corrected for the effects of adsorption using Scale implemented in CrystalClear. All structures were solved by direct methods (SHELXS) 7 and refined by full-matrix least squares (SHELXL). 29 Regions of diffuse solvent in the solvated structures were treated with the PLATON SQUEEZE routine.…”

Section: Methodsmentioning

confidence: 99%

“… 5 A detailed understanding of the interactions between guest molecules and the host material is of critical importance to the design of improved functional materials, and in situ diffraction methods have made significant advances in delivering detailed structural insights into host–guest binding interactions in MOFs and porous molecular solids. 6 In contrast, far fewer examples have been reported of permanently porous materials derived from metal–organic polyhedra (MOPs), 7 and many show weak intermolecular forces leading to structural collapse upon desolvation. 7g , 8 …”

Section: Introductionmentioning

confidence: 99%

Porous Metal–Organic Polyhedra: Morphology, Porosity, and Guest Binding

et al. 2020

View full text Add to dashboard Cite

Designing porous materials which can selectively adsorb CO 2 or CH 4 is an important environmental and industrial goal which requires an understanding of the host–guest interactions involved at the atomic scale. Metal–organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs (Cu-1a , Cu-1b , Cu-2 ), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra. Thus, for Cu-1a , the void fraction outside the cages totals 56% with only 2% within. The relative stabilities of these MOP structures are rationalized by considering their weak nondirectional packing interactions using Hirshfeld surface analyses. The exceptional stability of Cu-1a enables a detailed structural investigation into the adsorption of CO 2 and CH 4 using in situ X-ray and neutron diffraction, coupled with DFT calculations. The primary binding sites for adsorbed CO 2 and CH 4 in Cu-1a are found to be the open metal sites and pockets defined by the faces of phenyl rings. More importantly, the structural analysis of a hydrated sample of Cu-1a reveals a strong hydrogen bond between the adsorbed CO 2 molecule and the Cu(II)-bound water molecule, shedding light on previous empirical and theoretical observations that partial hydration of metal−organic framework (MOF) materials containing open metal sites increases their uptake of CO 2 . The results of the crystallographic study on MOP–gas binding have been rationalized using DFT calculations, yielding individual binding energies for the various pore environments of Cu-1a .

show abstract

Switchable gate-opening effect in metal–organic polyhedra assemblies through solution processing

Abstract: Assemblies of lantern-type metal–organic polyhedra are found to show gate-opening gas adsorption depending on how they are treated with solvents.

Cited by 41 publications

References 51 publications

A Multifunctional, Charge‐Neutral, Chiral Octahedral M₁₂L₁₂ Cage

A Multifunctional, Charge‐Neutral, Chiral Octahedral M₁₂L₁₂ Cage

Four-dimensional metal-organic frameworks

Porous Metal–Organic Polyhedra: Morphology, Porosity, and Guest Binding

Contact Info

Product

Resources

About

Switchable gate-opening effect in metal–organic polyhedra assemblies through solution processing

Abstract: Assemblies of lantern-type metal–organic polyhedra are found to show gate-opening gas adsorption depending on how they are treated with solvents.

Cited by 41 publications

References 51 publications

A Multifunctional, Charge‐Neutral, Chiral Octahedral M12L12 Cage

A Multifunctional, Charge‐Neutral, Chiral Octahedral M12L12 Cage

Four-dimensional metal-organic frameworks

Porous Metal–Organic Polyhedra: Morphology, Porosity, and Guest Binding

Contact Info

Product

Resources

About

A Multifunctional, Charge‐Neutral, Chiral Octahedral M₁₂L₁₂ Cage

A Multifunctional, Charge‐Neutral, Chiral Octahedral M₁₂L₁₂ Cage