Highly Efficient NMR Enantiodiscrimination of Chiral Octanuclear Metalla-Boxes in Polar Solvent

“…The resulting metallacycles andc ages often form in high or quantitative yields eliminate the need for column chromatography and other purification techniques. [8] Our previous work described O 2 reductionc atalyzed by a self-assembledcofacialp orphyrin prism that produced about 61 %H 2 Oa sahomogeneouse lectrocatalyst. [7] The syntheseso fc ofacialf ree base, Ni II ,a nd Zn II tetrapyridyl-porphyrin prismsh ave been established by Therrien and co-workers.…”

mentioning

confidence: 99%

Tuning the Activity of Heterogeneous Cofacial Cobalt Porphyrins for Oxygen Reduction Electrocatalysis through Self‐Assembly

Oldacre

Crawley

Friedman

et al. 2018

Chemistry A European J

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We report a suite of coordination-driven self-assembled prisms for heterogeneous electrocatalytic oxygen reduction (ORR) differing in the molecular clips linking two porphyrin faces in a cofacial arrangement. ORR activities and selectivities of monomeric CoTPyP along with cofacial prisms Ox-Co, Oxa-Co, and Benzo-Co were probed using cyclic voltammetry and rotating ring-disk techniques. All species were immobilized as heterogeneous catalysts on glassy carbon electrodes using a Nafion ink method. The selectivities of Ox-Co, Oxa-Co, and Benzo-Co prisms towards H O as determined by RRDE were 87, 97, and 75 %, respectively. The current density of the Oxa-Co plateaus at five times that of Pt/C when normalized per Co/Pt. The high synthetic yield (79 %), competitive overpotential (η ≈800 mV) and high selectivity (%H O ≈97 %) of the Oxa-Co highlights how self-assembly can be used to address multi-electron multi-proton transformations using polynuclear catalysts.

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“…In this respect, several strategies can be employed to prepare larger metalla-assemblies, the tridentate tpt ligands can be replaced with larger tridentate [44,45] or even by tetradentate ligands to form octanuclear species [46], the dinuclear dihydroxy-l,4-benzoquinonato or naphthoquinonato arene ruthenium connectors can be replaced by macrocyclic dinuclear systems [47] or analogous hydroxy-benzoquinones with appendages [48], and the arene ligands can be also functionalized [49]. Indeed, to better exploit the EPR effect, even larger watersoluble metalla-assemblies can be envisaged.…”

Section: Exploiting the Enhanced Permeability And Retention Effectmentioning

confidence: 99%

Discrete Metalla‐Assemblies as Drug Delivery Vectors

Therrien¹

2013

Nanomaterials in Drug Delivery, Imaging, and Tissue Engineering

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The last decade has seen the field of metalla-assemblies moving towards applications. Not only are we still seeing beautiful new two-and threedimensional constructions appearing in the literature at a regular pace, but nowadays we also observe metalla-assemblies with functions. Indeed, metalla-assemblies are being used as micro-reactors, sensors or as molecular flasks, just to name some examples. Nevertheless, another application for metalla-assemblies capable of encapsulating guest molecules is emerging: The ability of some metalla-assemblies to act as water-soluble containers to solubilize and protect guest molecules in biological media has been explored, thus offering new opportunities in the fascinating field of coordination-driven self-assembly.In this chapter, an overview of metalla-assemblies acting as drug carriers is presented. Advantages and limitations of these systems from a biological point of view, and potential perspectives for these systems, is also discussed.

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Highly Efficient NMR Enantiodiscrimination of Chiral Octanuclear Metalla-Boxes in Polar Solvent

Abstract: Summary: Self-assembly of 5,10,15,20-tetra(4-pyridyl)porphyrin (tpp-H 2 ) and 5,10,15,20-tetra(4-pyridyl)porphyrinZn(II) (tpp-Zn) tetradentate panels with the dinuclear pcymene ruthenium clips [Ru 2 (η 6

Cited by 53 publications

References 42 publications

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Tuning the Activity of Heterogeneous Cofacial Cobalt Porphyrins for Oxygen Reduction Electrocatalysis through Self‐Assembly

Discrete Metalla‐Assemblies as Drug Delivery Vectors

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