Search results for "Dynamic covalent chemistry"

Helicate Extension as a Route to Molecular Wires

2008

We describe the preparation of a helicate containing four closely spaced, linearly arrayed copper(I) ions. This product may be prepared either directly by mixing copper(I) with a set of precursor amine and aldehyde subcomponents, or indirectly through the dimerization of a dicopper(I) helicate upon addition of 1,2-phenylenediamine. A notable feature of this helicate is that its length is not limited by the lengths of its precursor subcomponents: each of the two ligands wrapped around the four copper(I) centers contains one diamine, two dialdehyde, and two monoamine residues. This work thus paves the way for the preparation of longer oligo- and polymeric structures. DFT calculations and elec…

An Unlockable-Relockable Iron Cage by Subcomponent Self-Assembly

2008

Dynamic formation of hybrid peptidic capsules by chiral self-sorting and self-assembly.

2014

Owing to their versatility and biocompatibility, peptide-based self-assembled structures constitute valuable targets for complex functional designs. It is now shown that artificial capsules based on β-barrel binding motifs can be obtained by means of dynamic covalent chemistry (DCC) and self-assembly. Short peptides (up to tetrapeptides) are reversibly attached to resorcinarene scaffolds. Peptidic capsules are thus selectively formed in either a heterochiral or a homochiral way by simultaneous and spontaneous processes, involving chiral sorting, tautomerization, diastereoselective induction of inherent chirality, and chiral self-assembly. Self-assembly is shown to direct the regioselectivit…

Reversible Covalent and Supramolecular Functionalization of Water-Soluble Gold(I) Complexes.

2017

The ligation of gold(I) metalloamphiphiles with biomolecules is reported, using water-soluble AuI -N-alkynyl substituted maleimide complexes. For this purpose, two different polar ligands were applied: 1) a neutral, dendritic tetraethylene glycol-functionalized phosphane and 2) a charged, sulfonated N-heterocyclic carbene (NHC). The retro Diels-Alder reaction of a furan-protected maleimide gold(I) complex, followed by cycloaddition with a diene-functionalized biotin under mild conditions leads to a novel gold(I) metalloamphiphile. The strong streptavidin-biotin binding affinity in buffered aqueous solution of the resulting biotin alkynyl gold(I) phosphane conjugate remains intact. The cytot…

Binding Profiles of Self-Assembled Supramolecular Cages from ESI-MS Based Methodology

2018

Confined molecular environments have peculiar characteristics that make their properties unique in the field of biological and chemical sciences. In recent years, advances in supramolecular capsule and cage synthesis have presented the possibility to interpret the principles behind their self‐assembly and functions, which has led to new molecular systems that display outstanding properties in molecular recognition and catalysis. Herein, we report a rapid method based on ESI‐MS to determine the binding profiles for linear saturated dicarboxylic acids in a series of different cages. The cages were obtained by self‐assembly of modified tris(pyridylmethyl)amine (TPMA) complexes and diamines cho…

Cover Picture: An Unlockable-Relockable Iron Cage by Subcomponent Self-Assembly (Angew. Chem. Int. Ed. 43/2008)

2008

Fast Pirouetting Motion in a Pyridine Bisamine-Containing Copper-Complexed Rotaxane

2013

The present work reports the introduction of pyridine bisamine terdentate ligands in the structure of a pirouetting copper rotaxane. Rotaxane 2[PF6] constitutes the first example of the incorporation of imine-based dynamic covalent chemistry in the synthesis of switchable copper-complexed interlocked systems. In this rotaxane, the substitution of the classical terpyridine terdentate unit by a pyridine bisamine moiety has led to a significant stabilization of the pentacoordinated site. That fact has been evidenced by EPR spectroscopy and cyclic voltammetry. Regarding the tetracoordinated site, the congestion around the coordination sphere has been reduced to accelerate the typically slow reo…