Dataset Information

Secondary Bracing Ligands Drive Heteroleptic Cuboctahedral Pd^II₁₂ Cage Formation.

ABSTRACT: The structural complexity of self-assembled metal-organic capsules can be increased by incorporating two or more different ligands into a single discrete product. Such complexity can be useful, by enabling larger, less-symmetrical, or more guests to be bound. Here we describe a rational design strategy for the use of subcomponent self-assembly to selectively prepare a heteroleptic cage with a large cavity volume (2631 Å³) from simple, commercially available starting materials. Our strategy involves the initial isolation of a tris(iminopyridyl) Pd^II₃ complex 1, which reacts with tris(pyridyl)triazine ligand 2 to form a heteroleptic sandwich-like architecture 3. The tris(iminopyridyl) ligand within 3 serves as a "brace" to control the orientations of the labile coordination sites on the Pd^II centers. Self-assembly of 3 with additional 2 was thus directed to generate a large Pd^II₁₂ heteroleptic cuboctahedron host. This new cuboctahedron was observed to bind multiple polycyclic aromatic hydrocarbon guests simultaneously.

SUBMITTER: Espinosa CF

PROVIDER: S-EPMC10176475 | biostudies-literature | 2023 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Secondary Bracing Ligands Drive Heteroleptic Cuboctahedral PdII12 Cage Formation.

Espinosa Carles Fuertes CF Ronson Tanya K TK Nitschke Jonathan R JR

Journal of the American Chemical Society 20230428 18

The structural complexity of self-assembled metal-organic capsules can be increased by incorporating two or more different ligands into a single discrete product. Such complexity can be useful, by enabling larger, less-symmetrical, or more guests to be bound. Here we describe a rational design strategy for the use of subcomponent self-assembly to selectively prepare a heteroleptic cage with a large cavity volume (2631 Å3) from simple, commercially available starting materials. Our str ...[more]

PMID: 37115100

Similar Datasets

Project description:The encapsulation of molecular guests into supramolecular hosts is a complex molecular recognition process in which the guest displaces the solvent from the host cavity, while the host deforms to let the guest in. An atomistic description of the association would provide valuable insights on the physicochemical properties that guide it. This understanding may be used to design novel host assemblies with improved properties (i.e., affinities) toward a given class of guests. Molecular simulations may be conveniently used to model the association processes. It is thus of interest to establish efficient protocols to trace the encapsulation process and to predict the associated magnitudes ΔGbind and ΔGbind⧧. Here, we report the calculation of the Gibbs energy barrier and Gibbs binding energy by means of explicit solvent molecular simulations for the [Ga4L6]12- metallocage encapsulating a series of cationic molecules. The ΔGbind⧧ for encapsulation was estimated by means of umbrella sampling simulations. The steps involved were identified, including ion-pair formation and naphthalene rotation (from L ligands of the metallocage) during the guest's entrance. The ΔGbind values were computed using the attach-pull-release method. The results reveal the sensitivity of the estimates on the force field parameters, in particular on atomic charges, showing that higher accuracy is obtained when charges are derived from implicit solvent quantum chemical calculations. Correlation analysis identified some indicators for the binding affinity trends. All computed magnitudes are in very good agreement with experimental observations. This work provides, on one side, a benchmarked way to computationally model a highly charged metallocage encapsulation process. This includes a nonstandard parameterization and charge derivation procedure. On the other hand, it gives specific mechanistic information on the binding processes of [Ga4L6]12- at the molecular level where key motions are depicted. Taken together, the study provides an interesting option for the future design of metal-organic cages.

Dataset Information

Secondary Bracing Ligands Drive Heteroleptic Cuboctahedral Pd^II₁₂ Cage Formation.

Publications

Secondary Bracing Ligands Drive Heteroleptic Cuboctahedral Pd<sup>II</sup><sub>12</sub> Cage Formation.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets