Dioxastilbenophanes—synthesis and charge transfer complexation studies

Intramolecular McMurry coupling of dialdehydes derived from xylenyl dibromide and 4-hydroxy benzaldehyde afforded cis-stilbenophanes along with cyclophane diols. Stilbenophanes with a large cavity were also synthesized. Charge transfer complexations of the stilbenophanes with TCNE, TCNQ and PQT were studied. Some stilbenophanes form a relatively stronger complex with PQT rather than with TCNE and TCNQ.     

Ditopic hexaazamacrocycles containing pyridine: synthesis, protonation and complexation studies

Structural studies of metal complexes of five ditopic hexaazamacrocycles containing two pyridine rings ([n]py2N4 n= 18, 20, 22, 24 and 26) have been carried out. The synthesis of macrocycles [22]- to [26]-py2N4 are also reported. The protonation constants of the last three compounds and the stability constants of their complexes with Ni2+, Cu2+, Zn2+, and Pb2+ were determined at 25 degrees C in 0.10 mol dm(-3) KNO3 in aqueous solution. Our results with [22]py2N4 show significant differences from those described previously, while [24]py2N4 has not been studied before and [26]py2N4 is a new compound. Mononuclear and dinuclear complexes of the divalent metal ions studied with [22]- to [26]-py2N4 were found in solution. The stability constants for the ML complexes of the three ligands follow the Irving-Williams order: NiL2+ < CuL2+ > ZnL2+ > PbL2+, however for the dinuclear complexes the values for Pb2+ complexes are higher than the corresponding values for the Ni2+ and the Zn2+ complexes. The X-ray single crystal structures of the supramolecular aggregates [Cu2([20]py2N4)(H2O)4][Cu(H2O)6](SO4)3 x 3H2O and [Cu(2)([20]py(2)N4)(CH3CN)4][Ni([20]py2N4)]2(ClO4)8 x H2O, which are composed of homodinuclear [Cu2([20]py2N4])(H2O)4]4+ and [Cu2([20]py2N4])(CH3CN))4]4+, and mononuclear species, [Cu(H2O)6]2+ and [Ni([20]py2N4)]2+, respectively, assembled by an extensive network of hydrogen bonds, are also reported. In both homodinuclear complexes the copper centres are located at the end of the macrocycle and display distorted square pyramidal coordination environments with the basal plane defined by three consecutive nitrogen donors and one solvent molecule, water in and acetonitrile in . The macrocycle adopts a concertina-type conformation leading to the formation of macrocyclic cavities with the two copper centres separated by intramolecular distances of 5.526(1) and 5.508(7) A in 1a and 2a, respectively. The mononuclear complex [Ni([20]py2N4])]2+ displays a distorted octahedral co-ordination environment with the macrocycle wrapping the metal centre in a helical shape. EPR spectroscopy of the copper complexes indicated the presence of mono- and dinuclear species.     

Tri- and tetraurea piperazine cyclophanes: synthesis and complexation studies of preorganized and folded receptor molecules

A series of symmetrical tri‐ and tetrameric N‐ethyl‐ and N‐phenylurea‐functionalized cyclophanes have been prepared in nearly quantitative yields (86–99 %) from the corresponding tri‐ and tetraamino‐functionalized piperazine cyclophanes and ethyl or phenyl isocyanates. Their conformational and complexation properties have been studied by single‐crystal X‐ray diffraction, variable‐temperature NMR spectroscopy, and ESI‐MS analysis. The rigid 27‐membered trimeric cyclophane skeleton assisted by a seam of intramolecular hydrogen bonds results in a preorganized ditopic recognition site with an all‐syn conformation of the urea moieties that, complemented by a lipophilic cavity of the cyclophane, binds molecular and ionic guests as well as ion pairs. The all‐syn conformation persists in acidic conditions and the triprotonated triurea cyclophane binds an unprecedented anion pair, H₂PO₄^????HPO₄^2?, in the solid state. The tetra‐N‐ethylurea cyclophane is less rigid and demonstrates an induced‐fit recognition of diisopropyl ether in the solid state. The guest was encapsulated within the lipophilic interior of a quasicapsule, formed by intramolecular hydrogen‐bond‐driven folding of the 36‐membered cyclophane skeleton. In the gas phase, the essential role of the urea moieties in the binding was demonstrated by the formation of monomeric 1:1 complexes with K⁺, TMA⁺, and TMP⁺ as well as the ion‐pair complexes [KI+K]⁺, [TMABr+TMA]⁺ and [TMPBr+TMP]⁺. In the positive‐mode ESI‐MS analysis, ion‐pair binding was found to be more pronounced with the larger tetraurea cyclophanes. In the negative mode, owing to the large size of the binding site, a general binding preference towards larger anions, such as the iodide, over smaller anions, such as the fluoride, was observed.     

First synthesis and structure of beta-ketoimine calix[4]arenes: complexation and extraction studies

The synthesis of a new series of beta-ketoimine calix[4]arene derivatives is described. The reaction of calix[4]arene or p-tert-butylcalix[4]arene with bromoacetonitrile or bromobutyronitrile afforded di-, tri-, and tetranitrile calixarene derivatives (3-8, 3a), which were then reduced into the corresponding amine (9-13, 3b). The condensation of these aminocalixarenes with acetylacetone led to six beta-ketoimine calix[4]arene derivatives (14-18, 3c) as a class of selective receptors toward transition metals. Molecular structures of 4, 7, and 17 have been determined by X-ray diffraction. The packing of 17 revealed a network of intramolecular and intermolecular hydrogen bonds. The complexation properties of receptors 15, 17, and 3c toward different metal ions have been investigated by UV-vis titrations in organic media. The stoichiometries of complexes with 17 were determined by both the mole ratio method and Job plots. These novel receptors selectively complex Cu2+, Hg2+, and Ag+. Moreover, the extraction properties of 17 toward cations have been studied by liquid-liquid extraction and atomic absorption spectrometry. Compound 17 has good affinity and selectivity toward Pb2+.     

A new fluorescent double-cavity calix[4]arene: synthesis and complexation studies toward nitroanilines

A novel bicyclic calix[4]arene (4) molecular receptor has been synthesized, and its sensory abilities toward noxious aromatic nitroamines evaluated in apolar media. Molecular host–guest interactions examined through fluorescence and ¹H NMR spectroscopies showed the formation of 1:1 type endo-inclusion complexes with all the nitroaniline guests. The potential of 4 as a chemical sensor is established.     

A new cryptand: synthesis and complexation with paraquat

[formula: see text] Inspired by folded, nonpseudorotaxane complexes of bis(m-phenylene)-32-crown-10 systems, we synthesized a new bicyclic crown ether containing two 1,3,5-phenylene units linked by three tetra(ethyleneoxy) units. The new cryptand forms a "pseudorotaxane-like" inclusion complex with N,N'-dimethyl-4,4'-bipyridinium bis(hexafluorophosphate) with association constant Ka = 6.1 x 10(4) M-1, 100-fold greater than that of an analogous simple crown ether.     

Cyanuryl peptide nucleic acid: synthesis and DNA complexation properties

The synthesis of cyanuryl PNA monomer (CyaPNA) 6 was achieved by direct N-monoalkylation of cyanuric acid with N-(2-Boc-aminoethyl)-N′-(bromoacetyl)glycyl ethyl ester 4. Compound 6 was incorporated as a T-mimic into PNA oligomers and biophysical studies on their triplexes/duplex complexes with complementary DNA oligomers indicated unusual stabilization of PNA:DNA hybrids when the cyanuryl unit was located in the middle of the PNA oligomer.     

Heavy metal complexation by N-acyl(thio)urea-functionalized cavitands: synthesis, extraction and potentiometric studies

The synthesis and binding properties of resorcinarene-based cavitands functionalized with N-acylthiourea moieties towards different cations are described. Extraction studies with metal (Pb²⁺, Cu²⁺, Ag⁺, Hg²⁺, Cd²⁺, Eu³⁺, Fe³⁺, K⁺, Na⁺, and Ca²⁺) picrates and the incorporation in ion selective electrodes (ISEs), show that there is more than a 40% increase of the Ag⁺ extraction for N-acylthiourea ionophores (2, 3, and 8) in comparison with N-benzoyl-N′-benzylthiourea (9). Ionophore 8, which has a C₃ chain between the platform and the ionophore, extracts two times more Cu²⁺ than the more rigid one (2). Stoichiometry studies showed for ligand 2 a ligand/metal ratio of 1:1, while for model compound 9 a ratio of 1:2 was found. Potentiometric studies of electrodes revealed that cavitands 2, 3, and 8 induce a significantly different selectivity pattern compared to the cation-exchanger used, as well as model compound 9. Especially, a considerable enhancement of the selectivity towards Ag⁺ and Pb²⁺ over K⁺, Ca²⁺, and Na²⁺ ions was observed.     

New dioxadiaza- and trioxadiaza-macrocycles containing one dibenzofuran unit with two amino pendant arms: synthesis, protonation and complexation studies

New dioxadiaza- and trioxadiaza-macrocycles containing one rigid dibenzofuran unit (DBF) and N-(2-aminoethyl) pendant arms were synthesized, N,N'-bis(2-aminoethyl)-[17](DBF)N(2)O(2) (L(1)) and N,N'-bis(2-aminoethyl)-[22](DBF)N(2)O(3) (L(2)), respectively. The binding properties of both macrocycles to metal ions and structural studies of their metal complexes were carried out. The protonation constants of both compounds and the stability constants of their complexes with Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), and Pb(2+) were determined at 298.2 K, in aqueous solutions, and at ionic strength 0.10 mol dm(-3) in KNO(3). Mononuclear complexes with both ligands were formed, and dinuclear complexes were only found for L(2). The thermodynamic binding affinities of the metal complexes of L(2) are lower than those of L(1) as expected, but the Pb(2+) complexes of both macrocycles exhibit close stability constant values. On the other hand, the binding affinities of Cd(2+) and Pb(2+) for L(1) are very high, when compared to those of Co(2+), Ni(2+) and Zn(2+). These interesting properties were explained by the presence of the rigid DBF moiety in the backbone of the macrocycle and to the special match between the macrocyclic cavity size and the studied larger metal ions. To elucidate the adopted structures of complexes in solution, the nickel(II) and copper(II) complexes with both ligands were further studied by UV-vis-NIR spectroscopy in DMSO-H(2)O 1 : 1 (v/v) solution. The copper(II) complexes were also studied by EPR spectroscopy in the same mixture of solvents. The crystal structure of the copper complex of L(1) was also determined. The copper(II) displays an octahedral geometry, the four nitrogen atoms forming the equatorial plane and two oxygen atoms, one from the DBF unit and the other one from the ether oxygen, in axial positions. One of the ether oxygens of the macrocycle is out of the coordination sphere. Our results led us to suggest that this geometry is also adopted by the Co(2+) to Zn(2+) complexes, and only the larger Cd(2+) and Pb(2+) manage to form complexes with the involvement of all the oxygen atoms of the macrocyclic backbone.     

Chiral Schiff base derivatives of calix[4]arene: synthesis and complexation studies with chiral and achiral amines

Novel chiral Schiff base derivatives of calix[4]arenes 1–3 have been prepared from the reaction of 5,17-diformyl-25,27-dipropoxy-26,28-dihydroxycalix[4]arene 4 with (S)-(−)-1-phenylethylamine, (R)-(−)-1-cyclohexylethylamine, and (R)-(−)-2-heptylamine, respectively, by a convenient method in 69–80% yields. Spectrophotometric titrations have been performed in CHCl₃ at 20–30 °C in order to obtain the binding constants (K) and thermodynamic quantities (ΔH and ΔS) for the stoichiometric 1:1 inclusion complexation of various amines with these new host compounds. The molecular recognition abilities and enantioselectivity for guests (R)- and (S)-α-phenylethylamine, 3-morpholinopropylamine and n-butylamine are discussed from a thermodynamic point of view.     

Bis- and tris-(3-aminopropyl) derivatives of 14-membered tetraazamacrocycles containing pyridine: synthesis, protonation and complexation studies

New N-(3-aminopropyl) (L1, L2) and (2-cyanoethyl) (L3, L4) derivatives of a 14-membered tetraazamacrocycle containing pyridine have been synthesized. The protonation constants of L1 and L2 and the stability constants of their complexes with Ni2+, Cu2+, Zn2+ and Cd2+ metal ions were determined in aqueous solutions by potentiometry, at 298.2 K and ionic strength 0.10 mol dm(-3) in KNO3. Both compounds have high overall basicity due to the presence of the aminopropyl arms. Their copper(II) complexes exhibit very high stability constants, which sharply decrease for the complexes of the other studied metal ions, as usually happens with polyamine ligands. Mono- and dinuclear complexes are formed with L2 as well as with L1, but the latter exhibits mononuclear complexes with slightly higher K(ML) values while the dinuclear complexes of L2 are thermodynamically more stable. The presence of these species in solution was supported by UV-VIS-NIR and EPR spectroscopic data. The single crystal structures of [Cu(H2L2)(ClO4)]3+ and [CoL3Cl]+ revealed that the metal centres are surrounded by the four nitrogen atoms of the macrocycle and one monodentate ligand, adopting distorted square pyramidal geometries. In the [CoL3Cl]+ complex, the macrocycle adopts a folded arrangement with the nitrogen atom opposite to the pyridine at the axial position while in the [Cu(H2L2)(ClO4)]3+ complex, the macrocycle adopts a planar conformation with the three aminopropyl arms located at the same side of the macrocyclic plane.     

New strapped porphyrins as hosts for fullerenes: synthesis and complexation study

New strapped porphyrin-based hosts with different π-conjugated moieties and linkers have been prepared and their ability to bind with fullerenes was studied in dilute solution. We found that the ability of these hosts to bind with fullerenes strongly depends on their chemical nature and more precisely on the substitution pattern of the porphyrin deck. As expected, the more electron-rich hosts containing either an exTTF or a porphyrin unit as the strap bind fullerenes more efficiently with association constants of up to 3.9 × 10(5) M(-1). The results clearly demonstrate the potential of such hosts as a supramolecular scaffold for surface immobilization of pristine fullerenes.     

Novel triptycene-based cylindrical macrotricyclic host: synthesis and complexation with paraquat derivatives

[reaction: see text] A novel triptycene-based cylindrical macrotricyclic polyether containing two dibenzo[24]crown-8 cavities has been synthesized and proved to be a highly efficient host for the complexation with paraquat derivatives. Consequently, a new kind of very stable pseudorotaxane-type complex was formed in solution and in the solid state.     

Functionalized phosphorus derivatives of Salpen-like compounds: Synthesis and preliminary complexation studies

A new class of Salpen analogues based on phosphorus derivatives where the classical alkylene backbone has been replaced by a N-P-N linkage is described. Such linkage both affords a very good stability in water and an additional (fifth) potentially complexing site. The classical ortho-OH groups have been also replaced by various ortho-substituents, including diphenylphosphino groups. The synthesis of these compounds is easy and their structure can be varied at will at several levels. Several ways of synthesis can be used to combine the various fragments constituting these Salpen analogues. The structure of one of these fragments, an azide, was determined by X-ray crystallography. A preliminary study of the complexation ability of some of these new ligands was carried out with groups 10 (Ni) and 11 (Au) elements. Depending on the type of substituents and the type of metals used, these compounds can act as mono-, or tetra-dentate ligands.     

Bis- and tris-(methylphosphonic) acid derivatives of a 14-membered tetraazamacrocycle containing pyridine: synthesis, protonation and complexation studies

Two N-methylphosphonic acid derivatives of a 14-membered tetraazamacrocycle containing pyridine have been synthesized, H(4)L(1) and H(6)L(2). The protonation constants of these compounds and the stability constants of complexes of both ligands with Ni(2+), Cu(2+) and Zn(2+) were determined by potentiometric methods at 298 K and ionic strength 0.10 mol dm(-3) in NMe(4)NO(3). The high overall basicity of both compounds is ascribed to the presence of the phosphonate arms. (1)H and (31)P NMR spectroscopic titrations were performed to elucidate the sequence of protonation, which were complemented by conformational analysis studies. The complexes of these ligands have stability constants of the order of or higher than those formed with ligands having the same macrocyclic backbone but acetate arms. At pH = 7 the highest pM values were found for solutions containing the compound with three acetate groups, followed immediately by those of H(6)L(2), however, as expected, the increasing pH favours the complexes of ligands containing phosphonate groups. The single-crystal structure of Na(2)[Cu(HL(1))]NO(3)x8H(2)O has shown that the coordination geometry around the copper atom is a distorted square pyramid. Three nitrogen atoms of the macrocyclic backbone and one oxygen atom from one methylphosphonate arm define the basal plane, and the apical coordination is accomplished via the nitrogen atom trans to the pyridine ring of the macrocycle. To achieve this geometric arrangement, the macrocycle adopts a folded conformation. This structure seems consistent with Uv-vis-NIR spectroscopy for the Ni(2+) and the Cu(2+) complexes and with the EPR for the latter.     

Synthesis and metal ion complexation studies of proton-ionizable calix

A series of novel N-chromogenic calix[4]arene azacrown ethers were synthesized as selective extractants of potassium ion. 1,3-Alternate calix[4]arene azacrown ethers were prepared by reacting 25,27-dipropyloxy-26,28-bis(5-chloro-3-oxapentyloxy) calix[4]arenes with p-toluenesulfonamide in the presence of potassium carbonate. The coupling reaction of calix[4]arene azacrown ether with 2-hydroxy-5-nitrobenzyl bromide in the presence of triethylamine in THF gave the chromogenic calix[4]arene azacrown ether in moderate yield. These compounds show high potassium selectivity over other metal ions as shown by two-phase extraction, bulk liquid membrane, and 1H NMR studies on a ligand-metal complex. It is assumed that the OH of the chromogenic group attached on nitrogen can assist the complexation by encapsulation of the metal.     

Tripodal pseudopeptides with three histidine or cysteine donors: synthesis and zinc complexation

Peptide coupling of benzene-1,3,5-carboxylic acid with 3 equiv of histidine ethyl ester or cysteine ethyl ester has yielded the tripodal pseudopeptide ligands THB and H(3)TCB. Likewise, the combination of tris(carboxyethyl)nitromethane with 3 equiv of cysteine ethyl ester gave the tripod H(3)TCM. With zinc salts, the pseudopeptides form the insoluble compounds (THB)(2)Zn(5)Cl(10), Zn(3)(TCB)(2), and Zn(3)(TCM)(2) which are likely to be coordination polymers. Solution studies of THB with potentiometric methods have identified the complex species [(THB)(2)Zn](2+), [(THB)Zn-OH(2)](2+), and [(THB)Zn-OH](+). The pK(a) of the zinc-bound water molecule is 6.2, making the (THB)Zn complex a viable model of carbonic anhydrase.     

Crown-containing naphtho- and anthraquinones: synthesis and complexation with alkali and alkaline-earth metal cations

Novel naphtho- and anthraquinones conjugated with benzo- and dibenzo-18-crown-6 ethers were obtained. Their complexation reactions with Groups Ia and IIa metal perchlorates in acetonitrile were studied by spectrophotometric titration. In most cases, the complexation involves the crown ether moiety; the stability constant of the resulting complex decreases in the following order: Ba²⁺ > Sr²⁺ > Ca²⁺ > Na⁺. For crown-containing anthraquinone imines characterized by prototropic “imine-enamine” tautomerism, the complexation shifts the equilibrium toward the imine species, which allow these compounds to be classified among a rarely occurring type of tautomeric chromoionophores. Unlike other cations, the magnesium ions preferably interact with the heteroatoms of the anthraquinone moiety (the imine N atom, the OH group, and the carbonyl O atom of the benzamido group); the logK value reaches 4.4. The chelation to the Mg²⁺ cations and the effect of the complexation on the tautomeric equilibrium was confirmed by quantum chemical calculations.