Surface chemistry of metal–organic polyhedra

Albalad, Jorge; Hernández‐López, Laura; Carné‐Sánchez, Arnau; Maspoch, Daniel

doi:10.1039/d1cc07034g

Cited by 36 publications

(49 citation statements)

References 92 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[ 52 ] However, in some cases, such as with free amines and carboxylic acids, functionalized MOPs could not be directly synthesized, thus highlighting a demand for alternative approaches based on using protecting groups. [ 54 ] Interestingly, MOPs functionalized with coordinating groups can undergo supramolecular polymerization via self‐condensation reactions or upon coordination with additional metal ions. [ 42,55 ]…”

Section: Mops As Porous Building Blocks For Hierarchical Self‐assemblymentioning

confidence: 99%

“…Alternatively, our group previously developed a protection/deprotection strategy to synthesize the first‐ever (reported) example of a MOP bearing free carboxylic groups on its surface. [ 54 ] The synthesized cuboctahedral Rh‐MOP of formula [Rh 2 (BTC) 2 ] 12 (named COOH‐RhMOP ) was highly soluble in polar solvents such as DMF.…”

Section: Mops As Porous Building Blocks For Hierarchical Self‐assemblymentioning

confidence: 99%

“…The first pathway, and a rather straightforward one, is to invest more in developing new MOP cages with directional functionalities poised for extension chemistry, [ 54,96 ] whether by direct synthesis or post‐synthetic modification. As we previously mentioned, the design of functional MOPs with reactive surfaces had long been hampered by stability issues, which have recently been overcome with the advent new synthetic and post‐synthetic methodologies.…”

Section: Perspectivesmentioning

confidence: 99%

See 2 more Smart Citations

Metal–Organic Polyhedra as Building Blocks for Porous Extended Networks

et al. 2022

Self Cite

View full text Add to dashboard Cite

Metal-organic polyhedra (MOPs) are a subclass of coordination cages that can adsorb and host species in solution and are permanently porous in solid-state. These characteristics, together with the recent development of their orthogonal surface chemistry and the assembly of more stable cages, have awakened the latent potential of MOPs to be used as building blocks for the synthesis of extended porous networks. This review article focuses on exploring the key developments that make the extension of MOPs possible, highlighting the most remarkable examples of MOP-based soft materials and crystalline extended frameworks. Finally, the article ventures to offer future perspectives on the exploitation of MOPs in fields that still remain ripe toward the use of such unorthodox molecular porous platforms.

show abstract

Section: Mops As Porous Building Blocks For Hierarchical Self‐assemblymentioning

confidence: 99%

Section: Mops As Porous Building Blocks For Hierarchical Self‐assemblymentioning

confidence: 99%

Section: Perspectivesmentioning

confidence: 99%

See 1 more Smart Citation

Metal–Organic Polyhedra as Building Blocks for Porous Extended Networks

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…These two classes of cage molecules, CCs and MOCs, seem to have been individually investigated. Indeed, many review articles have recently been published on the development of these molecules [22][23][24][25][26][27][28][29][30][31][32][33], but in most cases they separately summarized the research of CCs or MOCs. This review aims to compare the synthetic and structural features of CCs and MOCs, identify common elements and characteristics between them, and unveil the specific mindsets, intuitions, techniques, and hidden tips in each field by meta-analysis of synthetic conditions and structural features extracted from published articles (Fig.…”

Section: Introductionmentioning

confidence: 99%

Coordination/Metal–Organic Cages Inside Out

Tateishi

Yoshimura

Tokuda

et al. 2022

Preprint

View full text Add to dashboard Cite

Cage-like molecules, assembled by the coordination of multiple metal ions and organic links, are pushing new frontiers in science due to their design flexibility and the resulting diverse and unique chemical properties. This field has been advanced by two close but distinct chemistry communities. Consequently, the family of molecules referred to as coordination cages (CCs) constituted of metal-pyridine coordination bonds or metal–organic cages (MOCs) based on dinuclear tetracarboxylates paddlewheel complexes in each community had not been reviewed cross-sectionally, even though they are conceptually similar. This review article extracted and compared experimental information on a total of 197 CCs and 78 MOCs from 182 reports to identify their synthetic and structural signatures. We did not merely enumerate the reports we collected; we meta-analyzed the data extracted from the reports and highlighted both the similarities and dissimilarities between CCs and MOCs. As a result, we clarified the key parameters governing the synthetic conditions. Furthermore, we identified a new research direction by visualizing unexplored features and properties of CCs and MOCs. This review article provides a good tutorial both for researchers attempting to cross the boundary between CCs and MOCs and those who are new to the field.

show abstract

“…Further, their molecular character enables the precise adjustment of their geometry, 6 composition, 7 and external surface functionalization. 8 The latter aspect is particularly relevant as it allows to adjust the hydrophilic/hydrophobic nature of the cages, 9 modify their solubility in different solvents, 10 improve their stability, 11 tune their acid/base properties, 12 and favor specific interactions with (bio)chemical systems. 13 Apart from fostering their use in solution, the control over MOPs surface functionalization also makes it possible to regulate their assembly in the solid state.…”

Section: Introductionmentioning

confidence: 99%

Reversible Discrete-to-Extended Metal–Organic Polyhedra Trans-formation by Sulfonic Acid Surface Functionalization

Troyano

Horike

Furukawa

2022

Preprint

View full text Add to dashboard Cite

Metal-organic polyhedra (MOPs) are molecular porous units in which desired functionalities can be installed with precise geometrical and compositional control. By combing two complementary chemical moieties, such as sulfonic acid group and Rh(II)-carboxylate paddlewheel, we synthesized a robust water-soluble cuboctahedral MOP with excellent features in both solution and solid state. Herein, we demonstrate that the superior chemical stability of the Rh2 unit and the elevated number of functional groups on the surface (24 per cage) result in a porous cage with high solubility and stability in water, including acidic, neutral and basic pH conditions. We also prove that the sulfonic acid-rich form of the cage can be isolated through post-synthetic acid treatment. This transformation involves an improved gas uptake capacity, and the capability to reversibly assemble the cages into a 3D metal-organic framework (MOF) structure. Likewise, this sulfonic acid functionalization provides both MOP and MOF solids with high proton conductivities (> 10-3 S cm-1), comparable to previously reported high conducting metal-organic materials. The influence of the MOP-to-MOF processing in the gas adsorption capacity indicates this structural transformation can provide materials with higher and more controllable porous properties. These results illustrate the high potential of acidic MOPs as more flexible porous building units in terms of processability, structural complexity and tunability of the properties.

show abstract

Surface chemistry of metal–organic polyhedra

Abstract: Metal-organic polyhedra (MOPs) are discrete, intrinsically-porous architectures that operate at the molecular regime and, owing to peripheral reactive sites, exhibit rich surface chemistry. Researchers have recently exploited this reactivity through...

Cited by 36 publications

References 92 publications

Metal–Organic Polyhedra as Building Blocks for Porous Extended Networks

Metal–Organic Polyhedra as Building Blocks for Porous Extended Networks

Coordination/Metal–Organic Cages Inside Out

Reversible Discrete-to-Extended Metal–Organic Polyhedra Trans-formation by Sulfonic Acid Surface Functionalization

Contact Info

Product

Resources

About