“Rim‐Differentiated” Pillar[6]arenes

Abstract

A "rim-differentiated" pillar[6]arene ) was obtained successfully, with the assistance of a dimeric silver trifluoroacetate template, among eight different constitutional isomers in a direct and regioselective manner. The solid-state conformation of this macrocycle could switch from the 1,3,5-alternate to a truly rim-differentiated one upon guest inclusion. This highly symmetric RD-P[6] not only hosts metal-containing molecules inside its cavity, but also can form a pillar[6]arene-C 60 adduct through co-crystallization on account of donor-acceptor interactions. The development of synthetic strategies to desymmetrize pillararenes offers new opportunities for engineering complex molecular architectures and organic electronic materials.

Solvent-Dependent Self-Assembly of a Pillar[5]arene-Based Poly-Pseudo-Rotaxane Linked and Threaded by Silver(I) Trifluoroacetate: A Double Role

“…58 Recently, a dimeric silver(I) trifluoroacetate template was used to synthesize a rim-differentiated pillar [6]arene by the Sue group. 59 Nevertheless, coordination networks incorporating pillararenes with entangled structures are almost an unexplored area so far. 11 In the present work, as depicted schematically in Figure 2, the combination of the di-armed pillar [5]arene L and silver(I) trifluoroacetate leads to the formation of a poly-pseudorotaxane 2 and represents the first example in which the same salt-type guest component is used to both thread and link the poly-pseudo-rotaxane product.…”

“…The ion-pair recognition of silver­(I) trifluoroacetate for a peralkylated pillar[5]­arene was reported by the Huang group . Recently, a dimeric silver­(I) trifluoroacetate template was used to synthesize a rim-differentiated pillar[6]­arene by the Sue group . Nevertheless, coordination networks incorporating pillararenes with entangled structures are almost an unexplored area so far …”

Catalysis enabled synthesis, structures, and reactivities of fluorinated S8-corona[n]arenes (n = 8–12)

“…1a) and this prevents rapid access to onward functionality divesification. [20][21][22][23][24] For such cases derivatisation is required, leading to longer synthetic routes, reduced overall efficiency and time-consuming chromatographic separations of multiple intermediates. Potentially, catalytic macrocyclisation of commercial C 6 F 6 (or a simple analogue thereof) offers an elegant solution to such problems, as both the macrocyclisation and subsequent derivatisation can potentially be achieved by simple C-F displacements in single-step reactions.…”

Responsive Supramolecular Devices Assembled from Pillar[5]arene Nanogate and Mesoporous Silica for Cargo Release

“…Pillararenes (P­[ n ]­A) are promiscuous molecules due to their versatile functionalization and ability to be used as hosts for several kinds and sizes of guest molecules by enlarging their cavities. − For biological applications, a variety of biocompatible pillararenes have been proposed by the judicious choice of functional groups. − In recent years, P­[ n ]­A have been widely explored as a component of drug delivery systems, e.g., vesicles, − micelles, nanoparticles, − and nanogates for switchable devices. ,− Previously, we demonstrated that cationic ammonium pillar[5]­arene can be used as a nanogate by interacting with spherical anionic MS nanoparticle surfaces, indicating that cationic-substituted pillar[5]­arenes are promising switchable components for blocking silica pores . To the best of our knowledge, N -methylimidazolium-pillar­[5]­arene (MIP5 + ) has not been explored as a cationic nanogate for MSNs.…”