Recent Developments in the Preparation and Chemistry of Metallacycles and Metallacages via Coordination

Cook, Timothy R.; Stang, Peter J.

doi:10.1021/cr5005666

Cited by 1,661 publications

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“…For the other compounds listed in Table 1, uptake was quantified by 1 H NMR spectroscopy after isolation and disassembly in CD 2 Cl 2 , as discussed above for BPA (Supplementary Figs 16-22). In initial reactions with TNT (entry 3), uptake into the host assemblies was not observed.…”

Section: Uptake and Release Of Molecular Organic Guestsmentioning

confidence: 99%

“…For entries 3-9 the concentration of substrate molecules in each assembly was calculated from the ratio of thiolate:substrate 1 These pores are large enough 32 to allow each of the molecular guests listed in Table 1 to diffuse from the bulk solution to O h -and T d -symmetry cavities buried deeply within the interior of the supraspheres. As such, the hydrophobic domain within each suprasphere is best described as a percolated network of hydrophobic holes.…”

Section: A Percolated Network Of Hydrophobic Holesmentioning

confidence: 99%

“…Each 200 nm assembly contains hydrophobic cavities between the estimated 27,400 gold building blocks that are connected to one another by nanometre-sized pores. This gives a percolated network that effectively absorbs large numbers of molecules from water, including 600,000, 2,100,000 and 2,600,000 molecules (35, 190 and 234 g l ) of para-dichorobenzene, bisphenol A and trinitrotoluene, respectively.H ost-guest phenomena that involve the uptake of gases and small molecules are associated with the supramolecular chemistry of soluble capsules, cages and containers [1][2][3][4][5] or, alternatively, with heterogeneous reactions of porous solid-state materials such as zeolites 6 and metal-organic frameworks 7 . Only now, however, are organized assemblies of metal nanoparticles beginning to serve in a similar capacity as hosts for molecular guests.…”

mentioning

confidence: 99%

“…H ost-guest phenomena that involve the uptake of gases and small molecules are associated with the supramolecular chemistry of soluble capsules, cages and containers [1][2][3][4][5] or, alternatively, with heterogeneous reactions of porous solid-state materials such as zeolites 6 and metal-organic frameworks 7 . Only now, however, are organized assemblies of metal nanoparticles beginning to serve in a similar capacity as hosts for molecular guests.…”

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confidence: 99%

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Host–guest chemistry with water-soluble gold nanoparticle supraspheres

et al. 2016

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The uptake of molecular guests, a hallmark of the supramolecular chemistry of cages and containers, has yet to be documented for soluble assemblies of metal nanoparticles. Here we demonstrate that gold nanoparticle-based supraspheres serve as a host for the hydrophobic uptake, transport and subsequent release of over two million organic guests, exceeding by five orders of magnitude the capacities of individual supramolecular cages or containers and rivalling those of zeolites and metal-organic frameworks on a mass-per-volume basis. The supraspheres are prepared in water by adding hexanethiol to polyoxometalate-protected 4 nm gold nanoparticles. Each 200 nm assembly contains hydrophobic cavities between the estimated 27,400 gold building blocks that are connected to one another by nanometre-sized pores. This gives a percolated network that effectively absorbs large numbers of molecules from water, including 600,000, 2,100,000 and 2,600,000 molecules (35, 190 and 234 g l ) of para-dichorobenzene, bisphenol A and trinitrotoluene, respectively.H ost-guest phenomena that involve the uptake of gases and small molecules are associated with the supramolecular chemistry of soluble capsules, cages and containers [1][2][3][4][5] or, alternatively, with heterogeneous reactions of porous solid-state materials such as zeolites 6 and metal-organic frameworks 7 . Only now, however, are organized assemblies of metal nanoparticles beginning to serve in a similar capacity as hosts for molecular guests. In organic solvents, for example, light-induced dipoledipole interactions between gold nanoparticles with azobenzenefunctionalized thiolate ligands were recently used to entrap and catalyse the reactions of polar and alkylaromatic substrates 8 . By design, substrates were entrapped during nanoparticle aggregation to overcome the poor uptake and diffusion of molecular guests into colloidal nanocrystal assemblies. However, the uptake of molecular guests, a trait of supramolecular and solid-state chemistry, has so far not been achieved for colloidal nanoparticle assemblies.For that to occur, a thermodynamically favourable driving force must be combined with a porous structure whose interior architecture features host cavities, along with pathways for the effective diffusion of molecular guests from the exterior (bulk solution) to host domains deeply buried in the assembly's interior. If this were achieved, colloidal metal-nanoparticle assemblies could emerge as a new class of functional nano-engineered structures that are uniquely positioned between supramolecular containers and porous solid-state materials.We report a new class of functional assemblies, wherein the hydrophobic effect 9,10 drives the spontaneous uptake of alkyl and alkylaromatic guests 11 by porous 200 nm diameter supraspheres whose host capacities are orders of magnitude larger than those of individual cages or containers. On a mass-per-volume basis, the level of uptake rivals those of zeolites and metal-organic frameworks, which, for methane at elevated pressures, r...

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Section: Uptake and Release Of Molecular Organic Guestsmentioning

confidence: 99%

Section: A Percolated Network Of Hydrophobic Holesmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Host–guest chemistry with water-soluble gold nanoparticle supraspheres

et al. 2016

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“…By virtue of their hollow interiors, metal–organic container molecules1 offer great potential for a range of applications,2 including guest binding and separation, cavity‐controlled catalysis, and stabilization of reactive intermediates. In contrast to the many enantioselective transformations catalyzed inside an enzyme's (chiral) active site, in synthetic hosts the role of stereochemistry3 has received little attention, with the focus mostly on controlling the size of the host cavity to steer guest binding or catalysis 4.…”

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confidence: 99%

Quantification of Stereochemical Communication in Metal–Organic Assemblies

2016

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The derivation and application of a statistical mechanical model to quantify stereochemical communication in metal–organic assemblies is reported. The factors affecting the stereochemical communication within and between the metal stereocenters of the assemblies were experimentally studied by optical spectroscopy and analyzed in terms of a free energy penalty per “incorrect” amine enantiomer incorporated, and a free energy of coupling between stereocenters. These intra‐ and inter‐vertex coupling constants are used to track the degree of stereochemical communication across a range of metal–organic assemblies (employing different ligands, peripheral amines, and metals); temperature‐dependent equilibria between diastereomeric cages are also quantified. The model thus provides a unified understanding of the factors that shape the chirotopic void spaces enclosed by metal–organic container molecules.

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Bioinorganic supramolecular coordination complexes and their biomedical applications

Moreno‐Alcántar

Casini

2022

FEBS Letters

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The field of Bioinorganic Supramolecular Chemistry is an emerging research area including metal‐based supramolecules resulting from coordination‐driven self‐assembly (CDSA), whereby metal ions and organic ligands can be easily linked by metal–ligand bonds via Lewis' acid/base interactions. The focus of this ‘In a Nutshell’ review will be on the family of supramolecular coordination complexes, discrete entities formed by CDSA, which have recently captured widespread attention as a new class of versatile multifunctional materials with broad biological applications including molecular recognition, biosensing, therapy, imaging and drug delivery. Herein, we provide a summary of the state‐of‐the‐art use of these systems in biomedicine, with some selected representative examples, as well as our visions of the challenges and possible directions in the field.

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Recent Developments in the Preparation and Chemistry of Metallacycles and Metallacages via Coordination

Cited by 1,661 publications

References 388 publications

Host–guest chemistry with water-soluble gold nanoparticle supraspheres

Host–guest chemistry with water-soluble gold nanoparticle supraspheres

Quantification of Stereochemical Communication in Metal–Organic Assemblies

Bioinorganic supramolecular coordination complexes and their biomedical applications

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