ChemBridge (United States)

Ortho-functionalization of pillar[n]arenes has been a formidable challenge, partially due to the fragility of their macrocyclic skeletons. In this concise report, we describe a facile synthetic method for monoarylation/alkylation at the position ortho to the oxime functionality in pillar[4]arene[1]benzoquinone monoxime (1) via addition of Grignard reagents. The described method enables the creation of various mono-ortho-alkyl/aryl-substituted pillar[5]arene derivatives that were previously inaccessible.

Abstract CO is usually the dominant product on silver‐based catalysts in electrochemical CO2 reduction reaction (CO2RR) possibly due to weak *CO adsorption. In this report, a hydroxypillar[5]arene‐extended porous polymer‐confined silver catalyst (PAF‐PA5‐Ag‐0.8) for electrochemical CO2RR which can selectively produce ethanol with a maximum Faradaic efficiency of 55% at 11 mA cm−1 is described. The study reveals that the hydroxypillar[5]arene‐confined Ag clusters are the active sites for ethanol formation. Moreover, temperature‐programmed desorption measurements demonstrate an enhanced adsorption strength of CO* on PAF‐PA5‐Ag‐0.8 compared with that on commercial Ag nanoparticles, which is favored by the C‐C coupling to form ethanol. The density functional theory study indicates that the confined Ag clusters in PAF‐PA5‐Ag‐0.8 contribute to high C2 selectivity in CO2RR through facilitating *COOH formation, stabilizing *CO intermediates, and inhibiting hydrogen evolution. This work provides a new design strategy by modulating *CO adsorption strength on non‐copper electrocatalysts in converting CO2 into “green” C2 products.

In this letter, we report our fabrication of a three-dimensional hydroxy-rich pillar[5]arene-extended nanoporous aromatic framework PAF-P5-OH for CO2 uptake. CO2 adsorption study demonstrated that PAF-P5-OH exhibited excellent CO2 uptake capacity (88 cm3 g–1 at 273 K and 76 cm3 g–1 at 298 K) under atmospheric pressure, which could be attributed to the favored dipole interactions between the adsorbed CO2 molecules and the hydroxy groups in PAF-P5-OH.

Despite the fact that the rim and lateral functionalizations of pillar[n]arenes have been well explored, ortho-functionalization has rarely been realized. In this work, we report a facile method of introducing a single functionality ortho to the hydroxyl group in A1/A2-dihydroxypillar[5]arene via a Grignard addition to pillar[4]arene[1]quinone followed by a dienone-phenol rearrangement. The described ortho-alkylation/arylation method allowed formation of various mono ortho-alkyl/aryl-substituted A1/A2-dihydroxypillar[5]arenes previously difficult to obtain.

The adsorption process is widely used for the treatment of wastewater containing organic pollutants. We fabricated highly branched pillar[5]arene-based porous aromatic frameworks (PAFs), PAF-P5, for the adsorption and removal of organic pollutants (short-chain alkyl derivatives 1-3 and pesticide molecules 4-6) from water with high removal efficiency (RE). However, PAF-P5 was incapable of adsorbing aromatic organic dyes 7-9. Adsorption kinetic studies indicated that the adsorption is mainly driven by strong host-guest interactions between 1-3 and the pillar[5]arene units in PAF-P5, while 4-6 only weakly interacted with the pillar[5]arene units in PAF-P5. Moreover, chemically breaking down the pillar[5]arene rings in PAF-P5 caused changes in the pore size, the microenvironment inside of the pores, and the frame morphology, and the resultant frameworks, PAF-DeP5, exhibited poor adsorption toward 1-6 but adsorbed 7-9 possibly through physical adsorption as implied by fitting the experimental data into the adsorption kinetic models.

ABSTRACTThis report describes a facile method by which, without using any surface-assisted growth or pre-organisation, free-standing two-dimensional (2D) covalent organic monolayers (COMs) were synthesised through condensation reactions of planar tri-aldehydes with A1/A2-diamino-substituted pillar[5]arene (DAP5). In the as-formed monolayers (DAP5-COM-1 and DAP5-COM-2), the tubular pentagonal pillar[5]arene units positioned out of the 2D polymer planes suppress efficiently the interlayer π-π stacking interactions. Both DAP5-COM-1 and DAP5-COM-2 can be transferred onto solid surfaces for further characterisation and were found to possess unusual fluorescence up-conversion property.

Despite progress in the unidirectional complexation of cyclodextrins and calixarenes with nonsymmetric guests, unidirectional complexation using pillararenes as hosts remains scarcely explored. In this report, we describe the formation of unidirectional [2]pseudorotaxane-like complexes which were realized using n-alkyl alcohol guests and pillar[4]arene[1]benzoquinoneoxime made from pillar[4]arene[1]quinone in a selective monofunctionalizing manner.

Installation of m-benzoic acid functionalities on pillar[5]arene rims resulted in bis- and mono(m-benzoic acid)-functionalized pillar[5]arenes 1 and 2. Bis(m-benzoic acid)-functionalized pillar[5]arene 1 was able to self-assemble to form one-dimensional channels with DMF molecules residing in pillar[5]arene cavities. Esterification of two carboxylic acids in 1 with decane-1,10-diol did not afford a [1]catenane, but a bicyclic compound. Although 1-decanol esterification of mono(m-benzoic acid)-functionalized pillar[5]arene 2 did not form a self-included [1]pseudorotaxane-like structure, a mono(decyl m-benzoate)-functionalized pillar[5]arene bearing an ethyl acetate chain was found to form a self-included complex with the ethyl acetate moiety residing inside the pillar[5]arene cavity.

A shape-persistent cryptand 1, containing two face-to-face oriented electron-deficient 2,4,6-triphenyl-1,3,5-triazine units separated by approximately 7 Å, and bridged by two rigid 1,8-naphthyridine linkers and a pentaethylene oxide loop, is created for capturing polycyclic aromatic hydrocarbons. Cryptand 1 formed 1:1 complexes with PAH guest molecules, such as phenanthrene (6), anthracene (7), pyrene (8), triphenylene (9), and tetraphene (10). The single-crystal structure of complex 6⊂1 revealed that 6 was included in the cavity of 1 via face-to-face π···π stacking interactions. Soaking crystalline 1 in a toluene solution of anthracene resulted in anthracene from the toluene solution being picked up by the crystalline solid of 1.