The metal-driven self-assembly strategy is well-established for the construction of discrete architectures featuring a cavity. The resulting molecular rings and cages are potentially useful as hosts for complementary guests. Recent years have seen growing interest in the introduction of given functionalities, including redox properties which, among others, allow modulating the ionic charge of the cavity. Depending on which subunit is electroactive, various situations can be encountered, with a global redox activity which is ligand- and/or metal-centered and which involves or not electronic interactions between the constituting units. In this feature article, we propose to survey those different situations by exploring some recent examples of the growing family of redox-active self-assembled rings and cages.
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http://dx.doi.org/10.1039/c5cc00597c | DOI Listing |
Protein Sci
May 2024
Center for Cooperative Research in Biomaterials (CIC biomaGUNE), Basque Research and Technology Alliance (BRTA), Donostia-San Sebastián, Spain.
Enzyme scaffolding is an emerging approach for enhancing the catalytic efficiency of multi-enzymatic cascades by controlling their spatial organization and stoichiometry. This study introduces a novel family of engineered SCAffolding Bricks, named SCABs, utilizing the consensus tetratricopeptide repeat (CTPR) domain for organized multi-enzyme systems. Two SCAB systems are developed, one employing head-to-tail interactions with reversible covalent disulfide bonds, the other relying on non-covalent metal-driven assembly via engineered metal coordinating interfaces.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
April 2024
Univ Angers, CNRS, MOLTECH-ANJOU, F-49000, Angers, France.
Incorporating chiral elements in host-guest systems currently attracts much attention because of the major impact such structures may have in a wide range of applications, from pharmaceuticals to materials science and beyond. Moreover, the development of multi-responsive and -functional systems is highly desirable since they offer numerous benefits. In this context, we describe herein the construction of a metal-driven self-assembled cage that associates a chiral truxene-based ligand and a bis-ruthenium complex.
View Article and Find Full Text PDFNanoscale
August 2023
Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy.
Understanding the behaviour of self-assembled systems, from nanoscale building blocks to bulk materials, is a central theme for the rational design of high-performance materials. Herein, we revealed, at different length scales, how the self-assembly of TEMPO-oxidised cellulose nanocrystals (TOCNCs) into rod fractal gels is directed by the complexation of Fe ions on the surface of colloidal particles. Different specificities in Fe binding on the TOCNC surface and conformational changes of the nanocellulose chain were unveiled by paramagnetic NMR spectroscopy.
View Article and Find Full Text PDFJ Am Chem Soc
October 2022
Department of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn-Str. 6, 44227 Dortmund, Germany.
The field of anion recognition chemistry is dominated by two fundamental approaches to design receptors. One relies on the formation of covalent bonds resulting in organic and often neutral host species, while the other one utilizes metal-driven self-assembly for the formation of charged receptors with well-defined nanocavities. Yet, the combination of their individual advantages in the form of charge-neutral metal-assembled bench-stable anion receptors is severely lacking.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2022
Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036, India.
The discrete multinuclear Ag -NHC complexes [Ag (1) )](X) ; (n=3 or 4, X=BF , PF ), synthesized from a bis-NHC ligand 1 and Ag ions via multiligand self-assembly, were observed to be in equilibrium between two forms (tri- and tetranuclear) in solution on the NMR timescale, which is unprecedented in C -donor based chemistry. The existence of both the species was confirmed by various studies such as NMR ( H, VT, 2D-DOSY) and ESI-MS analysis along with concentration studies. Importantly, replacing Ag with other coinage metals (Au and Cu ) was found to alter the phenomenon entirely: a slow exchange from the tetra- to trinuclear species was noticed for the Au complexes (4 a, b), whereas no such process was detected in case of the Cu complexes (5 a, b).
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