Arene Framework Research Articles

Post-Synthetic Modification of Calix[4]arene Framework by Iridium-Mediated Alkyne Insertion into an Inert C-C Bond: A Novel Strategy for Unsymmetrical Macrocycles.

As a novel synthetic method for unsymmetrical macrocycles, we herein developed a post-synthetic modification of calix[4]arenes by insertion of a terminal alkyne into an inert C(methylene)-C(aryl) bond of the macrocyclic framework. In this transformation, C-iridated calix[4]arenes, readily synthesized through C-H bond activation of the parent calix[4]arene, undergoes C(methylene)-C(aryl) bond cleavage followed by insertion of an alkyne to provide a ring-expanded calix[4]arene complex. Removal of the iridium metal from the resulting complex was readily accomplished by a simple treatment with an acid. The developed sequential method affords novel unsymmetrical, monofunctionalized macrocyclic compounds via 3 steps from the parent calix[4]arene in good yield. The unique unsymmetrical structures of the alkyne-inserted macrocycles were evaluated by X-ray single crystal analyses. On the basis of theoretical calculations, we propose a reaction mechanism involving an uncommon C-C bond cleavage step through δ-carbon elimination for the ring enlargement process.

BHOEOCC6/n-dodecane: A new solvent extraction media for Cs removal from nuclear waste without using any phase modifier

Modifier-free diluent is most advantageous in hydrometallurgical route for separation of any radioactive element from high level liquid waste (HLLW). However there is not even a single calix crown reported in the literature that is soluble in pure n-dodecane and shows very high Cs extraction from such high nitric acid condition of 4.0 M prevalent in HLLW. Herein we designed a new calix crown-6-ether with an aim to reduce polarity so as to increase solubility in n-dodecane for extraction of Cs by density functional theory (DFT). The theoretically designed calix crown has been synthesised by introducing two 2-(hexyloxy)ethoxy alkyl arms at 1, 3 position calix[4]-arene framework and abbreviated as BHOEOCC6. Characterisation of BHOEOCC6 was carried out using 1H NMR, 13C NMR, and ESI-MS etc. techniques. 0.1 M BHOEOCC6/n-dodecane mixture shows exceptionally high stability as well as high Cs extraction ability (DCs = 10.75 @ 4.0 M HNO3) from highly acidic nuclear waste solution. The mechanism and interaction of Cs with BHOEOCC6 were also probed by experimental distribution ratio studies and instrumental techniques of UV–VIS titration and NMR studies of Cs-BHOEOCC6 complex.

Assembly of cobalt-p-sulfonatothiacalix[4]arene frameworks with phosphate, phosphite and phenylphosphonate ligands

Abstract Three cobalt-calixarene coordination frameworks, namely, {[Co4Cl(H4TC4AS)]4(HPO3)8}4− (CIAC-253), {[Co4Cl(H4TC4AS)]4(PO4)8}12− (CIAC-254) and {[Co4Cl(H4TC4AS)]3(Ph-PO3)6}3− (CIAC-255) were obtained by solvothermal reaction of a cobalt salt, sodium p-sulfonatothiacalix[4]arene (Na4H4TC4AS) and phosphate, phosphite and phosphonate ligands. In CIAC-253 and CIAC-254, the shuttlecock-like Co4Cl-(TC4AS) secondary building units (SBUs) are bridged by HPO3 2− or PO4 3− anions into two quadrilateral frameworks while in CIAC-255, the Co4Cl-(TC4AS) SBUs are linked into a triangular framework by phenylphosphonate anions. The supramolecular interactions between the phenyl groups of phosphonate and TC4AS play a crucial role in the formation of the triangle. Magnetic measurements revealed that all the cobalt(II) centers exhibit antiferromagnetic interactions.

Thioderivatives of Resorcin[4]arene and Pyrogallol[4]arene: Are Thiols Tolerated in the Self-Assembly Process?

Three novel thiol bearing resorcin[4]arene and pyrogallol[4]arene derivatives were synthesized. Their properties were studied with regards to self-assembly, disulfide chemistry, and Brønsted acid catalysis. This work demonstrates that (1) one aromatic thiol on the resorcin[4]arene framework is tolerated in the self-assembly process to a hexameric hydrogen bond-based capsule, (2) thio-derivatized resorcin[4]arene analogs can be covalently linked through disulfides, and (3) the increased acidity of aromatic thio-substituent is not sufficient to replace HCl as cocatalyst for capsule catalyzed terpene cyclizations.

High adsorption and separation performance of CO2 over N2 in azo-based (N=N) pillar[6]arene supramolecular organic frameworks* *Project supported by Shandong Province Higher Education Science and Technology Program, China (Grant No. J17KA016), State Key Laboratory of Bio- Fibers and Eco-Textiles (Grant No. K2019-12), and the Cultivation Fund of Henan Normal University, China (Grant No. 2020PL15).

Azo-based pillar[6]arene supramolecular organic frameworks are reported for CO2 and N2 adsorption and separation by density functional theory and grand canonical Monte–Carlo simulation. Azo-based pillar[6]arene provides suitable environment for CO2 adsorption and selectivity. The adsorption and selectivity results show that introducing azo groups can effectively improve CO2 adsorption and selectivity over N2, and both CO2 adsorption and CO2 selectivity over N2 follow the sequence pillar[6]arene_N4 > pillar[6]arene_N2 > pillar[6]arene. Pillar[6]arene_N4 exhibits CO2 adsorption capacity of ∼ 1.36 mmol/g, and superior selectivity of CO2 over N2 of ∼ 116.75 with equal molar fraction at 1 bar (1 bar = 105 Pa) and 298 K. Interaction analysis confirms that both the Coulomb and van der Waals interactions between CO2 with pillar[6]arene frameworks are greater than that of N2. The stronger affinity of CO2 with pillar[6]arene_N4 than other structures and the larger isosteric heat differences between CO2 and N2 rendered pillar[6]arene_N4 to present the high CO2 adsorption capacity and high CO2 selectivity over N2. Our results highlight the potential of azo-functionalization as an excellent means to improve pillar[6]arene for CO2 capture and separation.

Visualization and quantitation of electronic communication pathways in a series of redox-active pillar[6]arene-based macrocycles

While oxidized pillar[5]arenes with 1-5 benzoquinone units are known, very few examples of oxidized pillar[6]arenes have been reported. We describe here the synthesis, characterization and electrochemical behavior of a series of macrocyclic hosts prepared by the stepwise oxidation of 1,4-diethoxypillar[6]arene, resulting in high-yield and high-purity isolation of two constitutional isomers for each macrocycle, in which two, three or four 1,4-diethoxybenzene units are replaced by benzoquinone residues. A careful structural comparison with their counterparts in the pillar[5]arene framework indicates that the geometries of the macrocycles are better described as non-Euclidean hyperbolic hexagons and elliptic pentagons, respectively. A comprehensive computational study to determine anisotropic induced current density (ACID) allows us to visualize and quantify through-space and through-bond communication pathways along the macrocyclic belt. Experimental and simulated voltammetric data, as well as UV-vis spectra, of the new macrocycles afford insights into the various electronic communication pathways in these compounds.

Polyoxometalate-Incorporated Metallacalixarene@Graphene Composite Electrodes for High-Performance Supercapacitors.

Composites of polyoxometalate (POM)/metallacalixarene/graphene-based electrode materials not only integrate the superiority of the individual components perfectly but also ameliorate the demerits to some extent, providing a promising route to approach high-performance supercapacitors. Herein, first, we report the preparations, structures, and electrochemical performance of two fascinating POM-incorporated metallacalixarene compounds [Ag5(C2H2N3)6][H5 ⊂ SiMo12O40] (1) and [Ag5(C2H2N3)6][H5 ⊂ SiW12O40] (2); (C2H2N3 = 1 H-1,2,4-triazole). Single-crystal X-ray diffraction analyses illustrated that both 1 and 2 possess intriguing POM-sandwiched metallacalix[6]arene frameworks. Nevertheless, our investigations, including the electrochemical cyclic voltammetry, galvanostatic charge-discharge tests, and electrochemical impedance spectroscopy, reveal that the oxidation ability of the Keggin ions is a primary effect in electrochemical performance of these POM-incorporated metallacalixarene compounds. Namely, the electrodes containing Mo as metal atoms in the Keggin POM shows much higher capacitance than the corresponding W-containing ones. Moreover, compound 1@graphene oxide (GO) composite electrodes are fabricated and systematically explored for their supercapacitor performance. Thanks to the synergetic effects of GO and POM-incorporated metallacalixarenes, the compound 1@15%GO-based electrode exhibits the highest specific capacitance of up to 230.2 F g-1 (current density equal to 0.5 A g-1), which is superior to majority of the reported POM-based electrode materials.

Exploratory studies into 3d/4f cluster formation with fully bridge-substituted calix[4]arenes

Calix[4]arenes are extremely versatile ligands that are capable of supporting the formation of a wide variety of polymetallic clusters of paramagnetic metal ions. One can exert influence over cluster formation through alteration of the calix[4]arene framework and subsequent ‘expansion’ of the lower-rim polyphenolic binding site. The present contribution investigates cluster formation with calix[4]arenes substituted at all four methylene bridge positions with furan moieties. Two known cluster types have been isolated with this ligand, the structures of which lend insight into factors that may ultimately preclude the formation of mixed-metal species.

AuI⋅⋅⋅AuI Interaction Assisted Host–Guest Interactions and Stimuli‐Responsive Self‐Assembly in Tetranuclear Alkynylgold(I) Calix[4]arene‐Based Isocyanide Complexes

Multi-stimuli-responsive tetranuclear gold(I) complexes were prepared based on a tetra(alkynyl)calix[4]arene framework, with incorporation of a series of isocyanide ligands of tunable hydrophilicity. This class of complex was found to exhibit high sensitivity towards group IIIA metal ions especially In3+ . Drastic electronic absorption and emission changes were observed, which could be attributed to the formation of AuI ⋅⋅⋅AuI interactions during the binding event. Solvent-induced self-aggregation was also observed upon changing the solvent environment to a more polar medium, with the formation of nanoaggregates and the turning-on of the aurophilic interactions, leading to interesting luminescence and morphological changes. The aggregation process was monitored by UV/Vis absorption, emission and 1 H NMR spectroscopy and dynamic light scattering (DLS) studies, and the morphological changes were studied by electron microscopy. This new class of complex has shown high sensitivity towards external stimuli and demonstrated the feasibility of employing the on-off switching of aurophilicity as an effective design strategy for the construction of functional supramolecular systems.

A novel hybrid macrocyclic receptor based on bile acid and calix[4]arene frameworks for metal ion recognition

Abstract A novel hybrid macrocyclic receptor based on bile acid and calix[4]arene has been synthesized using the α-face of the bile acid and cone-conformation of calix[4]arene. Metal recognition properties of receptor were investigated. The receptor showed the strongest affinity for Hg2+ in acetonitrile. The stoichiometry of the Receptor:Hg2+ was 1:1.

Phosphonate monoesters on a thiacalix[4]arene framework as potential inhibitors of protein tyrosine phosphatase 1B.

Monoester derivatives of thiacalix[4]arene tetrakis(methylphosphonic) acid were found to be capable of inhibiting protein tyrosine phosphatase 1B. In addition, these compounds can strongly bind to human serum albumin.

Metal-promoted intermolecular electron transfer in tetrathiafulvalene-thiacalix[4]arene conjugates and tetrachlorobenzoquinone.

In this work, two series of tetrathiafulvalene (TTF) and thiacalix[4]arene (TCA) conjugates (TTF-TCA) were designed by CuAAC click reactions. The results obtained from NMR and (1)H NMR NOE indicated that their conformations of thiacalix[4]arene framework may prefer to 1,3-alternate. The cyclic voltammograms of four TTF-TCA compounds containing electroactive TTF units were provided. Meanwhile, their intermolecular electron-transfer (ET) behaviors with tetrachlorobenzoquinone (Q) mediated by different metal ions, Sc(3+), Pb(2+), Ag(+), Cd(2+), and Zn(2+), in CH3CN-CH2Cl2 (V/V = 1:1) solution were studied and analyzed via UV-vis spectroscopy. It was determined that intermolecular ET between each TTF-TCA and Q ensemble was not observed without introduction of the metal ions mentioned above. The added specified metal ions most likely induced the intermolecular ET between TTF-TCA and Q ensemble, and the effects of Sc(3+) functions were the most imperative. The intermolecular ET also proved to be reliant on the structure of TTF-TCA, where TTF-TCA 7a and 7b were more effective than TTF-TCA 6a and 6b. The difference may be credited to TTF-TCA 7a or 7b possessing two independent TTF pendants and providing a more synergic coordination among the TTF radical cation and Q radical anion with a metal ion.

Synthesis, structure, and properties of nitronyl nitroxyl tetraradical with calix[4]arene framework

A reaction of calix[4]arene tetraaldehyde with 2,3-bis(hydroxyamino)-2,3-dimethylbutane in DMF resulted in the corresponding 1,3-dihydroxyimidazolidine tetraadduct, whose oxidation gave a calix[4]arene (1,3-alternate) bearing four nitronyl nitroxyl-containing substituents at the upper rim.

Tri-substituted hexahomotrioxacalix[3]arene derivatives bearing imidazole units: synthesis and extraction properties for cations and chromate anions

The article describes the synthesis and extraction properties of the new hexahomotrioxacalix[3]arenebased derivatives cone- and partial-cone-2 bearing 1-methyl-1H-imidazole moieties at the lower rim. It has been demonstrated that O-alkylation of the flexible macrocycle 1 with 2-(chloromethyl)-1-methyl-1Himidazole hydrochloride affords tri-O-alkylated products with a cone or partial-cone conformation. Alkali metal salts such as NaH and Cs2CO3 can play an important role in the conformer distribution via a template effect. The conformation of receptors 2 has been confirmed by X-ray crystallographic analysis. Furthermore, the complexation properties of receptors 2 toward selected alkali/transition metal cations and alkylammonium ions are reported. The new 1-methyl-1H-imidazole-substituted hexahomotrioxacalix[3] arene frameworks are also efficient extractors of HCr2O7(-)/Cr2O7(2-) anions at low pH.

An excellent copper selective chemosensor based on calix[4]arene framework

The article depicts a detailed study regarding copper selective chemosensing and complexation nature of 5,11,17,23-tetrakis[(N,N-diphenylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (PAC4). Its photophysical characteristics in various solvents of different polarities along with the influence of acid and base on its spectral properties in these solvents are also discussed. The complexation affinity of PAC4 with regard to its latent applications as Cu(II) selective colorimetric and fluorescent sensor among the selected series of various cations such as Li(I), Na(I), K(I), Rb(I), Ba(II), Sr(II), Al(III), Fe(III), Cd(II), Co(II), Hg(II), Mn(II), Ni(II), Pb(II) and Zn(II) was examined by UV–visible and fluorescence emission spectroscopy in dichloromethane:acetonitrile (DCM:MeCN) solvent system. In addition, the process of complexation has been investigated through Job's plot and it has been observed that the complex between PAC4 and Cu(II) is formed in 1:1 stoichiometric ratio. The complex formation between PAC4 and Cu(II) has also been confirmed by FT-IR spectroscopy and thermal gravimetric analysis (TGA).

Conformational control of electron-rich calix[6]arene skeleton by paraquat recognition

Calix[6]arene derivatives having electron-donating groups were designed and synthesized for the recognition of electron-deficient organic guests. These compounds exhibited relatively well-resolved 1H NMR spectra while most calix[6]arene derivatives reported previously showed broad spectra. The 1H NMR spectra clearly indicated that the studied calix[6]arene derivatives adopted a 1,2,3-alternate conformation as the dominant conformation. The hydroxy derivative formed a host–guest complex with paraquat molecule, in which the calix[6]arene framework exclusively adopted a cone conformation. Thus, an efficient conformational conversion from the 1,2,3-alternate to the cone conformation took place upon the host–guest complexation.

Metal‐Ion‐Promoted Electron Transfer between Tetrathiafulvalene and Quinone Units Within a Calix[4]arene Framework and Tuning through Coordination of the Neighboring Crown Ether with a Sodium Cation

A new calix[4]arene 1 with tetrathiafulvalene (TTF), quinone, and crown ether units in the lower rim was designed and synthesized with the aim to investigate the possibility to tune the metal-ion promoted electron transfer by coordination of the crown ether unit with additional metal ions. Both absorption and electron spin resonance (ESR) spectroscopic studies clearly indicate that electron transfer occurs efficiently from TTF to the quinone units in the presence of Sc(3+)/Pb(2+)/Zn(2+). Moreover, the intramolecular electron transfer within 1 induced by Zn(2+) can be switched off by addition of Na(+) and further turned on by addition of either Sc(3+) or Pb(2+).

Cyclometalated complexes derived from calix[4]arene bisphosphites and their catalytic applications in cross-coupling reactions

Palladium and platinum dichloride complexes of a series of symmetrically and unsymmetrically substituted 25,26;27,28-dibridged p- tert-butyl-calix[4]arene bisphosphites in which two proximal phenolic oxygen atoms of p- tert-butyl- or p-H-calix[4]arene are connected to a P(OR) (R = substituted phenyl) moiety have been synthesized. The palladium dichloride complexes of calix[4]arene bisphosphites bearing sterically bulky aryl substituents undergo cyclometalation by C–C or C–H bond scission. An example of cycloplatinated complex is also reported. The complexes have been characterized by NMR spectroscopic and single crystal X-ray diffraction studies. During crystallization of the palladium dichloride complex of a symmetrically substituted calix[4]arene bisphosphite in dichloromethane, insertion of oxygen occurs into the Pd–P bond to give a P,O-coordinated palladium dichloride complex. The calix[4]arene framework in these bisphosphites and their metal complexes adopt distorted cone conformation; the cone conformation is more flattened in the metal complexes than in the free calix[4]arene bisphosphites. Some of these cyclometalated complexes proved to be active catalysts for Heck and Suzuki C–C cross-coupling reactions but, on an average, the yields are only modest.

Synthesis of porphyrin conjugates based on conformationally rigid and flexible resorcin[4]arene frameworks

Porphyrin conjugates were synthesized based on conformationally rigid, bowl shaped cavitand, and flexible unfirm resorcin[4]arenes. The influence of the resorcin[4]arene fragment on the porphyrin fluorescence is investigated.

Synthesis and characterization of cationic cyclopalladated complexes derived from p- tert-butyl-calix[4]arene bisphosphite with nitrogen donors

A series of new cationic cyclopalladated complexes 2–6 have been synthesized from neutral cyclopalladated complex 1 of p- tert-butyl-calix[4]arene bisphosphite with various nitrogen donor ligands (acetonitrile, pyridine, aniline, ( R)-(+)-1-phenylethylamine and 4,4′-bipyridine) in presence of Ag(OSO 2CF 3) as a chloride scavenger. These cationic cyclopalladated complexes have been characterized by NMR spectroscopy. Single crystal X-ray diffraction studies performed on cationic cyclopalladated complexes 3 and 6 in solid state reveal nearly square planar geometry around the metal and distorted cone conformation of the calix[4]arene framework. These cationic cyclopalladated complexes based on hetero ligands having variable steric and electronic properties could be efficient catalysts for important organic transformation reactions.