Chiral binaphthylbisbipyridine-based copper(i) coordination polymer gels as supramolecular catalysts

Abstract

A novel class of chiral coordination polymer organogels, with multi-stimuli responsive properties and suitable for use as catalysts in 1,3-dipolar Huisgen cycloaddition reaction, are reported.

Triazolyl‐Based Molecular Gels as Ligands for Autocatalytic ‘Click’ Reactions

“…In contrastt oo ther reportedm etallogels applied as catalysts for the same reaction, the metal was coordinated once the gel was formed, which allowsfor the loading of other metals with affinity to triazole ligands without disturbing their capacity for gelation. [23] Furthermore, the formationo ft he metallogel in water or water/alcohol mixtures allow the study of the reactionu nder biological conditions. The factt hat these gelators are derived from amino acids constitutes an additional advantage for the use of these compounds as catalytic systemsf or bioconjugation click reactions, regarding their biodegradability andb iocompatibility.…”

“…As mentioned before,t he influence of the metal on the self-assembly of the gelator molecules was revealed for shorter carbon chain length gelator PhTzVal 3 ( Figure 3D). Although the presence of the metal is not the main driving force for gelation, as observedf or other reported metallogels, [22][23][27][28][29][30] the metal-ligand interactions have some influence on the self-assembly of the gelator.I th as already been reported that metal-ligand interactions could influence the gelation, resulting in multifunctional metallogels with new interesting properties that could not be achieved in organogels, such as optical, catalytic or magnetic properties. [31][32][33] The native gels andt he corresponding metallogels were also studied by circular dichroisms pectroscopy to gain deeper insight into the structurala rrangement of the resultants elf-assembled materials ( Figure 4).…”

“…[20,21] In the fieldo fc lick reactions, Liu and co-workersh ave reporteda nh ydrogelator that self-assembled intoh elical nanotubes in the presence of Cu II ,l eading to ac hiral catalystt hat was active for aD iels-Alder reaction, whereas Gao and co-workersr eported the application of chiral binaphthylbispyridine-based copper(I) metallogels as catalysts for the Huisgen 1,3-dipolar cycloaddition. [22,23] Herein, we report the design, synthesis, and catalytic performance of lowmolecular-weight gelators derived from amino acid l-valine, functionalized with triazole fragmentsa sas upramolecular mimic of the multivalent features of covalent polytriazole ligands such as TBTA. The catalytic activity of the synthesized compounds on the Huisgen 1,3-dipolar cycloaddition of alkynes and azides, asw ella st heir applicationi nt heir autocatalytic synthesis have also been investigated.…”

One-Dimensional Helical Homochiral Metal-Organic Framework Built from 2,2′-Dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic Acid

“…Tridentate chiral Schiff base ligands has been found to form 1D helical framework which allow highly enantioselective separation of racemic secondary alcohols by inclusion crystallization [47]. Chiral binaphthylbisbipyridine-based copper (I) coordination polymer gels for use as catalysts in 1,3-dipolar Huisgen cycloaddition reactions are also reported [48]. Herein, we report the synthesis and X-ray crystal structure of the one-dimensional helical homochiral MOF, (R)-MOF-2, constructed from (R)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid (2) (Scheme 2).…”

Generation of metallosupramolecular polymer gels from multiply functionalized grid-type complexes

“…11 Control of the emission characteristics of Cu(II), Pd(II) and Pt(II) complexes of 8-hydroxyquinoline ligands bearing lipophilic substituents has been achieved in a similar fashion. 12 Certain bis(bipyridyl)binaphthyl ligands 13 gelate organic solvents (and mixtures thereof) 14 With appropriate external functionalisation, it is possible to prepare grids that assemble into well-defined 1D-and 2D-architectures via metal ion coordination. 3,6 Further, the enhancement of ligand acidity resulting from metal ion coordination can allow such grids to be obtained in overall uncharged forms in principle suited to dispersion in non-polar media.…”