Incorporation of an A1/A2-Difunctionalized Pillar[5]arene into a Metal–Organic Framework

Abstract

An efficient synthetic route to an A1/A2-difunctionalized pillar[5]arene containing resolvable planar chirality has been developed and the arene employed as a strut in the synthesis of P5A-MOF-1, which has been demonstrated by X-ray powder diffraction analysis--supported by modeling--to be isoreticular with MOF-5. This metal-organic framework has an active domain that expresses good and selective uptake of neutral and positively charged electron-poor aromatic guests, which effect color changes of the cubic crystals from faint yellow to deep orange, arising from charge transfer between the guests and active domain of P5A-MOF-1.

Pillar-Shaped Macrocyclic Hosts Pillar[n]arenes: New Key Players for Supramolecular Chemistry

“…87 The A1/A2 dibromo-functionalized pillar [5]arene 42 [5] was first synthesized by cocyclization Scheme 12. Synthesis of Pillar [5]arenes Containing One, Two, and Three Benzoquinone Moieties by Ester/EtherSelective Oxidation Scheme 13.…”

Zn2+‐Triggered Drug Release from Biocompatible Zirconium MOFs Equipped with Supramolecular Gates

“…[24][25][26] The emergence of pillarenes (or pillararenes) [27][28][29][30][31][32] has been one of the most signifi cant achievements in supramolecular chemistry and materials science over the past 7 years. The superior structures, facile functionalization, and typical host-guest properties of pillarenes stimulated a tremendous upsurge of interest in artifi cial transmembrane channels, [ 33,34 ] drug nanocarriers, [35][36][37][38][39][40] gas sorption, [ 41,42 ] MOFs, [ 43 ] sensing and detection, [ 44 ] stabilization of nanoparticles, biological applications, [ 45,46 ] etc. [47][48][49][50][51] Herein, benign activation mechanisms have been applied to targeted drug release systems constructed from monodisperse nanoMOFs (NMOFs) and carboxylatopillar [5]arene (CP5)-based stimuli-responsive supramolecular gates for CNS disease therapy for the fi rst time ( Figure 1 ).…”

Pillarene‐Involved Metallic Supramolecular Nanostructures

“…[47] In 2012, Stoddart and coworkers reported the first example of porous metal-organic frameworks incorporating pillar [5]arene as active domains. [48] They synthesized an A1/A2-difunctionalized pillar [5]arene organic strut 4, which is conformationally rigid and a singlet for the remaining constitutionally hetereotopic methylene group lying on the C2 axis (Figure 3a). Heating a mixture of this ligand with Zn(NO 3 ) 2 •6H 2 O in DMF at 100 ℃ over 24 h produced a pillar [5]arene decorated porous framework P5A-MOF-4, which is isoreticular to MOF-5 ( Figure 3b).…”