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Exposing Mechanisms for Defect Clearance in Supramolecular Self-Assembly: Palladium–Pyridine Coordination Revisited
[Image: see text] Spherical three-dimensional (3D) cages composed of palladium(II) and pyridyl ligands are a mainstay of supramolecular chemistry with demonstrated catalytic and optoelectronic applications. The widely reported self-assembly of these palladium-based cages exhibits sensitivity to the...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10091417/ https://www.ncbi.nlm.nih.gov/pubmed/36961381 http://dx.doi.org/10.1021/acs.inorgchem.2c04404 |
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author | Poole, David A. Bobylev, Eduard O. de Bruin, Bas Mathew, Simon Reek, Joost N. H. |
author_facet | Poole, David A. Bobylev, Eduard O. de Bruin, Bas Mathew, Simon Reek, Joost N. H. |
author_sort | Poole, David A. |
collection | PubMed |
description | [Image: see text] Spherical three-dimensional (3D) cages composed of palladium(II) and pyridyl ligands are a mainstay of supramolecular chemistry with demonstrated catalytic and optoelectronic applications. The widely reported self-assembly of these palladium-based cages exhibits sensitivity to the solvents, reagents, and/or reactants employed. This sensitivity, and the resulting inconsistency between synthetic protocols, hinders the development of desirable palladium-based cages. We have found that pyridyl ligand substitution—the rate-limiting step of self-assembly—is facilitated by endogenous supporting ligands derived from the solvents, reagents, and reactants employed in synthetic protocols of palladium- and platinum-based assemblies. Here, we present a systematic investigation combining (1)H-NMR, electrospray ionization mass spectrometry (ESI—MS), and absorption spectroscopy to characterize the intermediates to support the mechanism of pyridyl ligand substitution on a model complex, M(py)(2) (M = (N,N,N′,N′-tetramethylethylenediamine)palladium(II), py = pyridine), under simulated synthetic conditions for self-assembly. Our investigation exposes mechanisms for pyridyl ligand substitution, featuring intermediates stabilized by solvent, anion, or (in situ formed) alkoxide moieties. Interrogation of destabilizing agents (2,2,2-trifluoroethanol and tetra(n-butyl)ammonium chloride) reveal similar mechanisms that ultimately facilitate the self-assembly of coordination cages. These findings rationalize widely reported solvent and anion effects in the self-assembly of coordination cages (and similar constructs) while highlighting methodologies to understand the role of supporting ligands in coordination chemistry. |
format | Online Article Text |
id | pubmed-10091417 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-100914172023-04-13 Exposing Mechanisms for Defect Clearance in Supramolecular Self-Assembly: Palladium–Pyridine Coordination Revisited Poole, David A. Bobylev, Eduard O. de Bruin, Bas Mathew, Simon Reek, Joost N. H. Inorg Chem [Image: see text] Spherical three-dimensional (3D) cages composed of palladium(II) and pyridyl ligands are a mainstay of supramolecular chemistry with demonstrated catalytic and optoelectronic applications. The widely reported self-assembly of these palladium-based cages exhibits sensitivity to the solvents, reagents, and/or reactants employed. This sensitivity, and the resulting inconsistency between synthetic protocols, hinders the development of desirable palladium-based cages. We have found that pyridyl ligand substitution—the rate-limiting step of self-assembly—is facilitated by endogenous supporting ligands derived from the solvents, reagents, and reactants employed in synthetic protocols of palladium- and platinum-based assemblies. Here, we present a systematic investigation combining (1)H-NMR, electrospray ionization mass spectrometry (ESI—MS), and absorption spectroscopy to characterize the intermediates to support the mechanism of pyridyl ligand substitution on a model complex, M(py)(2) (M = (N,N,N′,N′-tetramethylethylenediamine)palladium(II), py = pyridine), under simulated synthetic conditions for self-assembly. Our investigation exposes mechanisms for pyridyl ligand substitution, featuring intermediates stabilized by solvent, anion, or (in situ formed) alkoxide moieties. Interrogation of destabilizing agents (2,2,2-trifluoroethanol and tetra(n-butyl)ammonium chloride) reveal similar mechanisms that ultimately facilitate the self-assembly of coordination cages. These findings rationalize widely reported solvent and anion effects in the self-assembly of coordination cages (and similar constructs) while highlighting methodologies to understand the role of supporting ligands in coordination chemistry. American Chemical Society 2023-03-24 /pmc/articles/PMC10091417/ /pubmed/36961381 http://dx.doi.org/10.1021/acs.inorgchem.2c04404 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Poole, David A. Bobylev, Eduard O. de Bruin, Bas Mathew, Simon Reek, Joost N. H. Exposing Mechanisms for Defect Clearance in Supramolecular Self-Assembly: Palladium–Pyridine Coordination Revisited |
title | Exposing Mechanisms
for Defect Clearance in Supramolecular
Self-Assembly: Palladium–Pyridine Coordination Revisited |
title_full | Exposing Mechanisms
for Defect Clearance in Supramolecular
Self-Assembly: Palladium–Pyridine Coordination Revisited |
title_fullStr | Exposing Mechanisms
for Defect Clearance in Supramolecular
Self-Assembly: Palladium–Pyridine Coordination Revisited |
title_full_unstemmed | Exposing Mechanisms
for Defect Clearance in Supramolecular
Self-Assembly: Palladium–Pyridine Coordination Revisited |
title_short | Exposing Mechanisms
for Defect Clearance in Supramolecular
Self-Assembly: Palladium–Pyridine Coordination Revisited |
title_sort | exposing mechanisms
for defect clearance in supramolecular
self-assembly: palladium–pyridine coordination revisited |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10091417/ https://www.ncbi.nlm.nih.gov/pubmed/36961381 http://dx.doi.org/10.1021/acs.inorgchem.2c04404 |
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