Main-group-element calix[4]arenes: variable coordination and conformational isomerism at phosphorus and silicon

Treatment of calix[4]arene (1b) with trichloromethylsilane yields two conformers of calix[4]SiMe(OH), the cone 2b-C and the partial cone 2b-PC. These are isolated and structurally characterized, and their thermodynamic activation parameters are determined in solution [Ea = 117(3) kJ/mol, delta H = 5(4) kJ/mol]. Similar parameters are found for the p-tert-butylcalix[4]arene analogues 2a-C and 2a-PC. Deprotonation of 2b with butyllithium yields calix[4]SiMe(OLi) (8b). The structure of 8b is solvent dependent: 8b contains a five-coordinate silicon in THF and a four-coordinate silicon in benzene. Similar behavior is found for the p-tert-butylcalix[4]arene analogues. The five-coordinate phosphorus analogue of the anion in 8, p-tert-butylcalix[4]PMe (11a), is synthesized from the phosphonium triflate salt p-tert-butylcalix[4]PMe(OH)OTf (10a(OTf)) via treatment with butyllithium. The structure of 11a shows the geometry around phosphorus to be very close to a pure trigonal bipyramid. The X-ray structure of 10a(OTf) cannot be obtained, but its iodide analogue 10a(T) is synthesized and structurally characterized. The cation in 10a(I) adopts the partial cone conformation in the solid state, similar to 2b-PC. Treatment of 8b with methyl trifluoromethanesulfonate yields the methyl phenyl ether calix[4]SiMe(OMe) (3b). This species and its p-tert-butyl analogue 3a are structurally characterized. Both adopt the partial cone conformation. The SiMe group in 3b can be removed via treatment with fluoride to yield the monomethylated calix[4]arene 4b in 50-60% overall yield based on 1b.     

Stereoselective synthesis and optical resolution of chiral calix[4]arenes with mixed ligating functionalities

Exhaustive alkylation of syn-proximal bis[(2-pyridylmethyl)oxy]calix[4]arene 1 with t-butyl bromoacetate or 2-(chloromethyl)quinoline hydrochloride in the presence of Cs₂CO₃ affords selectively a new type of inherently chiral calix[4]arenes 2a,b in the partial cone conformation. (±) 2b has been resolved into its optical antipodes by an HPLC method.     

Partially O-alkylated thiacalix[4]arenes: synthesis, molecular and crystal structures, conformational behavior

NMR spectroscopy, X-ray diffraction analysis, and quantum chemical calculations were used for conformational behavior study of partially alkylated thiacalix[4]arenes bearing methyl (1), ethyl (2), or propyl (3) groups at the lower rim. The conformational properties are governed by two basic effects: (i) stabilization by intramolecular hydrogen bonds, and (ii) sterical requirements of the alkoxy groups at the lower rim. While the monosubstituted derivatives 1a and 3a adopt the cone conformation in solution, distally disubstituted compounds 1b, 1'b, 2b, 2'b, 3b, and 3'b exhibit several interesting conformational features. They prefer pinched cone conformation in solution, and, except for 3'b, they form also 1,2-alternate conformation, which is flexible and undergoes rather fast transition between two identical structures. The crystal structures of the compounds 1b, 2b, 2'b, and 3b revealed yet quite rare 1,2-alternate conformation forming molecular channels held together by pi-pi interactions. Different channels-with hexagonal symmetry, 0.26 nm wide-are formed in the crystal structure of the pinched cone conformation of 3b. An uncommon hydrogen bonding pattern was found in dimethoxy and dipropoxy derivatives 1'b and 3'b that adopt distorted cone conformations in crystal. Trialkoxy-substituted compounds 1c and 3c adopt the partial cone conformation in solution. A higher mobility of methyl derivative 1c enables also existence of the cone conformer.     

Calix[4]Arenes in the partial cone conformation as ionophores in silver ion-selective electrodes

Two calix[4]arene derivatives, in the partial cone conformation, with sulfur-containing functionalities, were tested as neutral carrier ionophores in potentiometric silver-selective electrodes of conventional membrane and membrane-coated glassy carbon electrode types. Comparison with a calix[4]arene in the cone conformation was made. The membranes were prepared using either 2-nitrophenyl octyl ether or bis(ethylhexyl)sebacate as plasticizers and potassium tetrakis(p-chlorophenyl)borate as the lipophilic salt in a poly(vinyl chloride) matrix. Both calix[4]arenes yielded electrodes of good sensitivity (approx. 47 mV dec⁻¹) in the range 10⁻⁴–10⁻¹ M and excellent selectivity [log K_Ag,_MH+ < −1.5] of transition, alkali and heavy metal cations, including sodium, mercury(II) and lead(II) cations. Temperature effects and reproducibility of response were determined and the interfering effects of mercury(II) and lead (II) ions on the membranes were noted. The partial cone conformation allows improved selectivity over certain cations relative to calix[4]arenes in the cone conformation.     

Bilayers, corrugated bilayers, and coordination polymers of p-sulfonatocalix[6]arene

Exploration into the host-guest supramolecular chemistry of p-sulfonatocalix[6]arene with pyridine N-oxide and 4,4'-dipyridine N,N'-dioxide has resulted in the characterization of three new structural motifs with the calixarene in the "up-down" double partial cone conformation. Two are hydrogen-bonded network structures formed with pyridine N-oxide and either nickel or lanthanide metal counterions (1 and 2, respectively). Complex 1 displays host-guest interactions between pyridine N-oxide and the calixarene in the presence of hexaaquanickel(II) counterions. Complex 2 demonstrates selective coordination modes for different lanthanides involving the calixarene and pyridine N-oxide. The third structure, 3, is a coordination polymer which is formed with 4,4'-dipyridine N,N'-dioxide molecules which span a hydrophilic layer and join lanthanide/p-sulfonatocalix[6]arene fragments. Although complexes 1-3 all have the calixarene in the "up-down" double partial cone conformation, 1 and 3 form bilayer arrangements within the extended structures while 2 forms a previously unseen corrugated bilayer arrangement.     

Conformationally Selective Synthesis of Mononitrocalix[4]arene in Cone or Partial Cone

Nitro‐substituted calixarenes in a cone and a partial cone conformation were prepared selectively using distinct synthetic routes. The selective nitration of tris‐ or penta‐substituted phenols of calix[4]arene or calix[6]arene provided mononitrocalix[n ]arenes (n  =  4, 6). Subsequent addition of ethylene glycol (EG) moieties to mononitrocalix[4]arene provided tetraEGylcalix[4]arene in locked partial cone conformation. By an alternative route – initial addition of EG moieties to the non‐derivatized calix[4]arene followed by the uncontrolled nitration – provided mononitro‐ and dinitro‐tetraEGylcalix[4]arenes locked in the cone conformation. These nitrocalix[4]arenes with locked cone or partial cone conformation are useful building blocks for further assembly of supramolecular systems, especially in the area of material sciences.     

Synthesis, structure and spectroscopic properties of calix[4]phloroglucinarene dodecamethyl ether and its trifluoroacetic acid complex

The action of trifluoroacetic acid (TFA) on 2,4,6-trimethoxybenzyl alcohol 3 affords the title tetrameric compound in high yield as a maroon TFA complex, 4; trituration of which with acetone gives the free, colorless, calix[4]phloroglucinarene (5) that can also be directly isolated by treating the reaction mixture with base. The novelty of compounds 4 and 5 is that they possess four additional methoxy groups, which occupy the cavity of the known calix[4]resorcinarene octamethyl ether (2). Ultraviolet-visible spectroscopic analysis shows that TFA-complex 4 exhibits transannular charge-transfer interactions between the opposite aromatic rings. The (1)H-NMR spectrum of the TFA-complex 4 does not change over a wide temperature range, strongly suggesting that it adopts a saddle (1,3-alternate) structure. The conformation of the free phloroglucinarene 5 is temperature-dependent, as determined by variable temperature (1)H NMR spectroscopy. Tetramer 5 adopts a partial cone conformation at low temperatures, but at elevated temperatures is similar to that of the TFA complex 4 (saddle). Tetramer 5 is conformationally mobile at ambient temperature, but generally has a flattened cone (boat) conformation. The ΔG(≠) for inversion in 5 between partial cone and boat conformation is 12.5 Kcal mol(-1), while that between boat and saddle conformation is 14.3 Kcal mol(-1). Conformational changes are also dependant on pH.     

Preparation and conformation of dioxocalix[4]arene derivatives

CrO(3) oxidation experiments conducted on atropisomeric forms of 2 (2(paco), 2(1,3)(-)(alt), and 2(1,2)(-)(alt)) indicate that under the reaction conditions only methylene groups located between pairs of geminal rings oriented in an anti disposition are oxidized to carbonyls. NMR data suggest that the tetrahydroxydioxocalix[4]arenes 7 and 9 adopt the partial cone and 1,2-alternate conformations, respectively. In the crystal structure of 7.2EtOAc the dioxocalixarene adopts a partial cone conformation, whereas 9 adopts in the crystal a 1,2-alternate conformation. In both conformations, pairs of geminal rings connected to a carbonyl are oriented in an anti fashion. The relative stability of the partial cone and 1,2-alternate conformations of 7 and 9 is underestimated by MM3 calculations. The topomerization barriers of 7 and 9 are 12.8 and 13.6 kcal mol(-)(1), respectively.     

Metal-organic anion receptors: arranging urea hydrogen-bond donors to encapsulate sulfate ions

A new class of synthetic receptors for anions can be prepared by arranging urea hydrogen-bond donor groups on a simple metal-organic scaffold. The complex cation [PtL4]2+ (L = 8-(n-butylurea)iso-quinoline) can adopt four conformations reminiscent of calix[4]arene-based receptors; "cone", "partial cone", "1,2-alternate", or "1,3-alternate". 1H NMR solution data and solid-state X-ray structures show that a "1,2-alternate" conformation is used to bind spherical halide ions while a "cone" conformation is involved in strong binding with the tetrahedral oxy-anions such as the sulfate ion; even in a strongly competitive solvent such as DMSO.     

一种新型杯[4]芳烃的合成

本文通过对特丁基杯[4]芳烃的酚羟基烷基化和苯环特丁基位上的IPSO-硝化制备了一系列对硝基杯[4]芳烃烷基醚,烷基分别是n-C~4H~9(3a)、n-C~8H~1~7(3b)、n-C~1~2H~2~5(3c)和n-C~1~6H~3~3(3d)。^1HNMR表明所有新的杯[4]芳烃都具有锥形(cone)构象。     

New artificial receptors from selectively functionalized calix[4]arenes

Abstract

The development of new synthetic methods for the monoalkylation of calix[4]arenes at the lower rim allows the synthesis of a new class of trihydroxamate siderophores. Three chelating hydroxamic acid units are introduced through a sequence of reactions which blocks the macrocycle in the cone conformation. The new ligands obtained form neutral 1:1 complexes (FeL) with iron (III), which are stable in EtOH/H₂O 9:1 at pH 2–7. Calix[4]arene bis-crown ethers are prepared by exploiting the selective 1,2-(proximal) functionalization of calix[4]arenes at the lower rim. These ligands are, however, less effective in complexing alkali metal cations compared with the 1,3-calix[4]arene crown-ethers which, in their partial cone structure, offer a better shielding for the complexed cations. Rigid upper rim-bridged calix[4]arenes potentially useful for the inclusion of neutral molecules are prepared by exploiting the selective 1,3-diformylation of calix[4]arene at the upper rim. Finally a new chloromethylation method for calix[4]arenes blocked in the cone conformation is described together with the synthesis of new cavitands.     

Synthesis of cone, partial-cone, and 1,3-alternate 25, 27-Bis

The preparation of 25,27-bis[1-(2-ethyl)hexyl]- and 25, 27-bis[1-(2-tert-butoxy)ethyl]calix[4]arene-crown-6 combining one polyether crown-6 and one alkylchain O-attached on each side of a calix[4]arene in the cone, partial-cone, and 1,3-alternate conformations are reported. The control over 25, 27-bisalkylcalix[4]arene-crown-6 conformation via varying specific reaction conditions was studied. The series of calix[4]arenes have been prepared by two routes, which differ in the order in which the alkyl or polyether groups were introduced. Moreover, methods have been developed to selectively prepare the cone and partial-cone conformers by using an appropriate base in the alkylation reactions. The conformations of these new derivatives have been probed by (1)H NMR analysis and X-ray crystallography. The (1)H and (13)C NMR spectra of 25,27-bis[1-(2-ethyl)hexyl]calix[4]arene-crown-6, 1, 3-alternate 1, cone 2, and partial-cone 3 are also discussed.     

Synthesis and Conformational Studies of Lower Rim Cyanomethyl Substituted Calix[4]arenes

The conformational inversion characteristics of calix[4]arenes carrying cyanomethyl groups on the lower rim have been investigated. Complete conversion from a 1,3-alternate to a partial cone conformation was observed for the 1,3-dicyanomethyl ether of calix[4]arene at room temperature, while at higher temperatures further inversion to a 1:1 mixture of partial cone and cone conformers occurred.     

Thiacalix[4]arene based reconfigurable molecular switches: set-reset memorized sequential device

The fluorescent chemosensors 3, 5 and 7 based on thiacalix[4]arene bearing naphthyl groups have been designed and synthesized. The optical chemosensor 3 based on a thiacalix[4]arene of cone conformation behaves as "turn-on" optical chemosensor for Fe(3+) and F(-) ions. However, chemosensors 5 and 7 based on a thiacalix[4]arene of 1,3-alternate conformation demonstrate "turn-on" optical behaviour for Hg(2+), F(-) ions (with receptor 5 as turn-on for K(+) ions also) and "turn-off" behaviour for Fe(3+) ions. The simultaneous presence of Fe(3+) and Hg(2+) or K(+) or F(-) ions results in formulation of reversible "on-off" switches. Various molecular logic gates developed in response to molecular switching between these chemical inputs have been integrated into sequential logic circuits with memory function in a feedback loop which mimics "set-reset" molecular level information processing device.     

Controlling the conformation and interplay of p-sulfonatocalix[6]arene as lanthanide crown ether complexes

Control over the conformational flexibility of p-sulfonatocalix[6]arene in the solid state is possible in the presence of varied stoichiometric amounts of [18]crown-6 and selected lanthanide(III) chlorides. Complexes 1 and 2 have the calixarene in the elusive up-up double cone conformation, whilst complex 3 has the calixarene in the centrosymmetric up-down double partial cone conformation, whereby it acts as a divergent receptor. Complex 1 has a double molecular capsule arrangement which is composed of two p-sulfonatocalix[6]arenes shrouding two [18]crown-6 molecules, also with both coordinated and homoleptic aquated lanthanide ions around the hydrophilic sulfonate rims of the calixarenes. Complex 2 has a ferris wheel arrangement with one lanthanide metal centre coordinated to a sulfonate group and another coordinated to the crown ether whilst tethered to a sulfonate group of the calixarene. Complex 3 forms from a solution with large excess of [18]crown-6, and possesses a crown ether molecule in each of the partial cones and has homoleptic aquated lanthanide ions involved in a complicated hydrogen-bonding regime within the extended structure.     

Solution and X-Ray Crystal Structures of the Di- and Tetra-allyl Ether of tert- utylcalix[4]arene

The di- and tetra-allyl ethers of tert-butylcalix[4]arene 1 and 2 have been prepared by alkylation of tert-butylcalix[4]arene with allyl bromide and K₂CO₃ using different reaction times. Solution ¹H NMR measurement of the di-allyl ether 1 and X-ray crystal structures of the complexes of 1 with chloroform (1a) or methanol (1b) indicate the cone conformation of 1 in which intramolecular hydrogen bonding can be maximized. The crystalline state conformers 1a and 1b are distorted in different grades depending on the solvent. While methanol is incorporated in the macrocycle, chloroform molecules do not occupy the cage. The solution ¹H NMR spectra of tetra-allyl ether 2 show the co-existence of the cone and partial cone conformation. The partial cone conformer of 2 was investigated by X-ray crystallography. In this compound hydrogen bonding is not existent. The conformer distribution is likely affected by steric and template effects.     

Synthesis and structure of bis(methylaluminium · HCCH3) p-tert-butylcalix[4]arene

Treatment of p-tert-butylcalix[4]areneH₄ iwth AlMe₃ in toluene at elevated temperature affords after work-up the complex {[MeAl(NCMe)]₂(p-tert-butylcalix[4]arene)}, which adopts a flattened partial cone conformation as characterized by X-ray crystallographu.     

Complexation of quaternary ammonium ions by tetraester derivatives of [3.1.3.1]homooxacalixarene in mobile and in fixed conformation

In the tetraalkylation of p-tert-butyl[3.1.3.1]homooxacalixarene with BrCH2CO2R and K2CO3 in acetone, the initially formed cone conformer is converted into the more stable 1,4-alternate conformer when R = Me or Et, but not when R = i-Pr or t-Bu. In the case of R = i-Pr, derivatives in fixed 1,4-alternate conformation and in partial cone conformation were also isolated. Compounds in fixed cone conformation are good ligands for tetramethylammonium, acetylcholine, and N-methylpyridinium salts in CDCl3, but the partial cone isomer proved to be somewhat better and even the 1,4-alternate conformer turned out to be active. The possible involvement of the ester functions as additional binding sites is discussed; moreover, an insight into the energetics of the complexation and conformational isomerization processes is given.     

Evidence of Hydrogen Bonding in Stabilizing the Cone Conformation of a Monoalkylated Calix[4]arene. X-ray Structure of 25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene

The synthesis of25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene3 as a byproduct of the preparation of 1,3-dialkylated25,27-di-[2-(ethoxy-1p-toluene-sulfonate)phenyl]-26,28-dihydroxy calix[4]arene 2 is reported. Compound 3 is a monoalkylatedcalix[4]arene in the cone conformation. The X-ray structure of 3 showed that this conformation is stabilized by intramolecular hydrogen bonding.     

Calixarene--poly(dithiophene)-based chemically modified electrodes

The stepwise synthesis of cone and partial cone 1,3-bridged n-propoxy-calix[4]crown ethers ("monomers" 2 and 3) with an electropolymerizable 2,2'-dithiophene-3-yl-hexylene functionality at the lower rim, is described. The potential of 2 and 3 as sensing agents for alkali metal ions was investigated by 1H NMR titration experiments with NaSCN and KSCN. The results obtained have confirmed that the presence of the heterocyclic subunit does not affect the well-known size-selectivity observed with calix[4]crowns. Monomers 2 and 3 were electropolymerized (Pt as a working electrode, CH2Cl2/CH3CN, Bu4NPF6) to produce the title chemically modified electrodes (CMEs). After coating with a PVC membrane containing a lipophylic cation exchanger, CMEs based on calix[4]-crown-5 2b (cone) and 3b (partial cone) were tested for the potentiometric recognition of alkali metal ions in aqueous solution. In agreement with NMR titration studies, a satisfactory potentiometric response in terms of K+/Na+ selectivity was obtained only with CME 2b (pK(K/Na) 1.51). The amperometric responses of PVC-uncoated CMEs were studied by cyclic voltammetry (CV) experiments in CH3CN solution. High Na- selectivity was found with the CME based on partial cone calix[4]crown-4 3a, and frequency response analysis (FRA) measurements support this finding.