An Integrated approach (thermodynamic, structural, and computational) to the study of complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative in acetonitrile

The calix[4]arene secondary-amide derivative L was synthesized, and its complexation with alkali-metal cations in acetonitrile (MeCN) was studied by means of spectrophotometric, NMR, conductometric, and microcalorimetric titrations at 25 °C. The stability constants of the 1:1 (metal/ligand) complexes determined by different methods were in excellent agreement. For the complexation of M(+) (M = Li, Na, K) with L, both enthalpic and entropic contributions were favorable, with their values and mutual relations being quite strongly dependent on the cation. The enthalpic and overall stability was the largest in the case of the sodium complex. Molecular and crystal structures of free L, its methanol and MeCN solvates, the sodium complex, and its MeCN solvate were determined by single-crystal X-ray diffraction. The inclusion of a MeCN molecule in the calixarene hydrophobic cavity was observed both in solution and in the solid state. This specific interaction was found to be stronger in the case of metal complexes compared to the free ligand because of the better preorganization of the hydrophobic cone to accept the solvent molecule. Density functional theory calculations showed that the flattened cone conformation (C(2) point group) of L was generally more favorable than the square cone conformation (C(4) point group). In the complex with Na(+), L was in square cone conformation, whereas in its adduct with MeCN, the conformation was slightly distorted from the full symmetry. These conformations were in agreement with those observed in the solid state. The classical molecular dynamics simulations indicated that the MeCN molecule enters the L hydrophobic cavity of both the free ligand and its alkali-metal complexes. The inclusion of MeCN in the cone of free L was accompanied by the conformational change from C(2) to C(4) symmetry. As in solution studies, in the case of ML(+) complexes, an allosteric effect was observed: the ligand was already in the appropriate square cone conformation to bind the solvent molecule, allowing it to more easily and faster enter the calixarene cavity.     

Selective interaction of lower rim calix[4]arene derivatives and bivalent cations in solution. Crystallographic evidence of the versatile behavior of acetonitrile in lead(II) and cadmium(II) complexes

The interaction of lower rim calix(4)arene derivatives containing ester (1) and ketone (2) functional groups and bivalent (alkaline-earth, transition- and heavy-metal) cations has been investigated in various solvents (methanol, N,N-dimethylformamide, acetonitrile, and benzonitrile). Thus, 1H NMR studies in CD3OD, C3D7NO, and CD3CN show that the interaction of these ligands with bivalent cations (Mg2+, Ca2+, Sr2+, Ba2+, Hg2+, Pb2+, Cd2+) is only observed in CD3CN. These findings are corroborated by conductance measurements in these solvents including benzonitrile, where changes upon the addition of the appropriate ligand (1 or 2) to the metal-ion salt only occur in acetonitrile. Thus, in this solvent, plots of molar conductance against the ligand/metal cation ratio reveal the formation of 1:1 complexes between these ligands and bivalent cations. Four metal-ion complex salts resulting from the interaction of 1 and 2 with cadmium and lead, respectively, were isolated and characterized by X-ray crystallography. All four structures show an acetonitrile molecule sitting in the hydrophobic cavity of the ligand. The mode of interaction of the neutral guest in the cadmium(II) complexes differs from each other and from that found in the lead(II) complexes and provides evidence of the versatile behavior of acetonitrile in binding processes involving calix(4)arene derivatives. The thermodynamics of complexation of these ligands and bivalent cations in acetonitrile is reported. Thus, the selective behavior of 1 and 2 for bivalent cations is for the first time demonstrated. The role of acetonitrile in the complexation process in solution is discussed on the basis of 1H NMR and X-ray crystallographic studies. It is suggested that the complexation of 1 and 2 with bivalent cations is likely to involve the ligand-solvent adducts rather than the free ligand. Plots of complexation Gibbs energies against the corresponding data for cation hydration show a selectivity peak which is explained in terms of the predominant role played by cation desolvation and ligand binding energy in complex formation involving metal cations and macrocycles in solution. A similar peak is found in terms of enthalpy suggesting that for most cations (except Mg2+) the selectivity is enthalpically controlled. The ligand effect on the complexation process is quantitatively assessed. Final conclusions are given highlighting the role of the solvent in complexation processes involving calix(4)arene derivatives and metal cations.     

IrII(ethene): metal or carbon radical?

One-electron oxidation of [(Me(n)tpa)Ir(I)(ethene)]+ complexes (Me(3)tpa = N,N,N-tri(6-methyl-2-pyridylmethyl)amine; Me(2)tpa = N-(2-pyridylmethyl)-N,N,-di[(6-methyl-2-pyridyl)methyl]-amine) results in relatively stable, five-coordinate Ir(II)-olefin species [(Me(n)tpa)Ir(II)(ethene)](2+) (1(2+): n = 3; 2(2+): n = 2). These contain a "vacant site" at iridium and a "non-innocent" ethene fragment, allowing radical type addition reactions at both the metal and the ethene ligand. The balance between metal- and ligand-centered radical behavior is influenced by the donor capacity of the solvent. In weakly coordinating solvents, 1(2+) and 2(2+) behave as moderately reactive metallo-radicals. Radical coupling of 1(2+) with NO in acetone occurs at the metal, resulting in dissociation of ethene and formation of the stable nitrosyl complex [(Me(3)tpa)Ir(NO)](2+) (6(2+)). In the coordinating solvent MeCN, 1(2+) generates more reactive radicals; [(Me(3)tpa)Ir(MeCN)(ethene)](2+) (9(2+)) by MeCN coordination, and [(Me(3)tpa)Ir(II)(MeCN)](2+) (10(2+)) by substitution of MeCN for ethene. Complex 10(2+) is a metallo-radical, like 1(2+) but more reactive. DFT calculations indicate that 9(2+) is intermediate between the slipped-olefin Ir(II)(CH(2)=CH(2)) and ethyl radical Ir(III)-CH(2)-CH(2). resonance structures, of which the latter prevails. The ethyl radical character of 9(2+) allows radical type addition reactions at the ethene ligand. Complex 2(2+) behaves similarly in MeCN. In the absence of further reagents, 1(2+) and 2(2+) convert to the ethylene bridged species [(Me(n)tpa)(MeCN)Ir(III)(mu(2)-C(2)H(4))Ir(III)(MeCN)(Me(3)tpa)](4+) (n = 3: 3(4+); n = 2: 4(4+)) in MeCN. In the presence of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxo), formation of 3(4+) from 1(2+) in MeCN is completely suppressed and only [(Me(3)tpa)Ir(III)(TEMPO(-))(MeCN)](2+) (7(2+)) is formed. This is thought to proceed via radical coupling of TEMPO at the metal center of 10(2+). In the presence of water, hydrolysis of the coordinated acetonitrile fragment of 7(2+) results in the acetamido complex [(Me(3)tpa)Ir(III)(NHC(O)CH(3)))(TEMPOH)](2+) (8(2+)).     

Biomimetic zinc funnel complexes based on calix[6]N3ArO ligands: an acid-base switch for guest binding

The coordination chemistry of Zn in an N(3)ArOH environment has been explored. The ligands are based on calix[6]arenes that present two imidazole arms and an amino phenol moiety at the narrow rim. Three different types of complexes have been characterized. One is dicationic with Zn(2+) coordinated to the three nitrogen atoms and to the oxygen of the phenol group of the calix[6]ligand. This complex is very sensitive to exogenous coordinating molecules and exists as a 5-coordinate species due to the endo-complexation of a guest. The second species is a monocationic complex for which the phenol group has been deprotonated. The resulting N(3)ArOZn complex can also bind a guest ligand albeit with a lower affinity than the dicationic complex. The third species is neutral. It can be obtained upon reaction with a base to yield a hydroxo complex or with an anion such as a chloride that coordinates the metal center from the outside of the calixarene cavity. The simultaneous binding of two anionic donors decreases the Zn Lewis acidity, allowing an impressive conformational reorganization of the system. One imidazole arm is released by the metal center. The other one undergoes self-inclusion into the pi-basic calixarene cavity because the low affinity of the metal center for neutral ligand does not allow the endo-coordination of an exogenous guest. Hence, the calix[6]N(3)ArOH-based Zn complexes act as an acid-base switch for guest binding. Several aspects of this system appear reminiscent of Zn-peptidases of the astacin and serralisin families.     

Fluorometric chemosensors. Interaction of toxic heavy metal ions Pb(II), Cd(II), and Hg(II) with novel mixed-donor phenanthroline-containing macrocycles: spectrofluorometric,conductometric, and crystallographic studies

The macrocycles L(1)-L(3) incorporating N(2)S(3)-, N(2)S(2)O-, and N(2)S(2)-donor sets, respectively, and containing the 1,10-phenanthroline unit interact in acetonitrile solution with heavy metal ions such as Pb(II), Cd(II), and Hg(II) to give 1:1 ML, 1:2 ML(2), and 2:1 M(2)L complex species, which specifically modulate the photochemical properties of the ligands. The stoichiometry of the complex species formed during spectrofluorometric titrations and their formation constants in MeCN at 25 degrees C were determined from fluorescence vs M(II)/L molar ratio data. The complexes [Pb(L(1))][ClO(4)](2).(1)/(2)H(2)O (1), [Pb(L(2))][ClO(4)](2).MeNO(2) (1a), [Pb(L(3))(2)][ClO(4)](2).2MeCN (1b), and [Cd(L(3))][NO(3)](2) (2b) were also characterized by X-ray diffraction studies. The conformation adopted by L(1)-L(3) in these species reveals the aliphatic portion of the rings folded over the plane containing the heteroaromatic moiety with the ligands trying to encapsulate the metal center within their cavity. In 1, 1a, and 2b the metal ion completes the coordination sphere by interacting with counteranion units and solvent molecules. On the contrary, the 1:2 complex 1b shows Pb(II) sandwiched between two symmetry-related molecules of L(3) reaching an overall [4N + 4S] eight-coordination.     

The extraction of thallium(I) and silver(I) ions with 1,3-alternate calix[4]arene derivatives

Tetraallyloxy and tetrabenzyloxy derivatives of calix[4]arenes in cone and 1,3-alternate conformations were synthesised and their capacity to extract thallium(I) and silver(I) ions was investigated. ??Low??-temperature single crystal X-ray structure determinations were recorded for two derivatives in which the calixarene conformation was that of an alternating cone, the aromatic rings lying closely quasi-parallel to the $ \overline{4} $ -axis of the cone. The structure of a tetraallyloxy derivative in the cone conformation was also determined in which a molecule of acetonitrile was included within the calixarene cavity.     

Encapsulation of cyanometalates by a tris-macrocyclic ligand tricopper(II) complex: syntheses, structural variation, and magnetic exchange coupling pathways

The reaction of [M(CN)(6)](3-) (M = Cr(3+), Mn(3+), Fe(3+), Co(3+)) and [M(CN)(8)](4-/3-) (M = Mo(4+/5+), W(4+/5+)) with the trinuclear copper(II) complex of 1,3,5-triazine-2,4,6-triyltris[3-(1,3,5,8,12-pentaazacyclotetradecane)] ([Cu(3)(L)](6+)) leads to partially encapsulated cyanometalates. With hexacyanometalate(III) complexes, [Cu(3)(L)](6+) forms the isostructural host-guest complexes [[[Cu(3)(L)(OH(2))(2)][M(CN)(6)](2)][M(CN)(6)]][M(CN)(6)]30 H(2)O with one bridging, two partially encapsulated, and one isolated [M(CN)(6)](3-) unit. The octacyanometalates of Mo(4+/5+) and W(4+/5+) are encapsulated by two tris-macrocyclic host units. Due to the stability of the +IV oxidation state of Mo and W, only assemblies with [M(CN)(8)](4-) were obtained. The Mo(4+) and W(4+) complexes were crystallized in two different structural forms: [[Cu(3)(L)(OH(2))](2)[Mo(CN)(8)]](NO(3))(8)15 H(2)O with a structural motif that involves isolated spherical [[Cu(3)(L)(OH(2))](2)[M(CN)(8)]](8+) ions and a "string-of-pearls" type of structure [[[Cu(3)(L)](2)[M(CN)(8)]][M(CN)(8)]](NO(3))(4) 20 H(2)O, with [M(CN)(8)](4-) ions that bridge the encapsulated octacyanometalates in a two-dimensional network. The magnetic exchange coupling between the various paramagnetic centers is characterized by temperature-dependent magnetic susceptibility and field-dependent magnetization data. Exchange between the CuCu pairs in the [Cu(3)(L)](6+) "ligand" is weakly antiferromagnetic. Ferromagnetic interactions are observed in the cyanometalate assemblies with Cr(3+), exchange coupling of Mn(3+) and Fe(3+) is very small, and the octacoordinate Mo(4+) and W(4+) systems have a closed-shell ground state.     

Experimental and computational studies of selective recognition of Hg2+ by amide linked lower rim 1,3-dibenzimidazole derivative of calix[4]arene: species characterization in solution and that in the isolated complex, including the delineation of the nanostructures

Amide linked lower rim 1,3-dibenzimidazole derivative of calix[4]arene, L has been shown to be sensitive and selective to Hg(2+) in aqueous acetonitrile solution based on fluorescence spectroscopy, and the stoichiometry of the complexed species has been found to be 1:1. The selectivity of L toward Hg(2+) has been shown among 11 M(2+) ions, viz., Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), Ca(2+), and Mg(2+) studied, including those of the mercury group and none of these ions impede the recognition of Hg(2+) by L. Role of the solvent on the recognition of Hg(2+) has been demonstrated. The role of calix[4]arene platform and the benzimidazole moieties in the recognition of Hg(2+) by L has been delineated upon performing such studies with five different molecules of relevance as reference molecular systems. The binding cores formed by the receptor L and the reference compounds have been established based on the single crystal XRD structures, and the preferential metal ion binding cores have been discussed. The binding of Hg(2+) with L has been further established based on (1)H and (13)C NMR, ESI MS, absorption, and fluorescence lifetime measurements. Some of these techniques have been used to establish the stoichiometry of the species formed. The complex species formed between L and Hg(2+) have been isolated and characterized and found to be 1:1 species even in the isolated complex. Whereas transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM) provided the nanostructural behavior of L, the TEM and SEM demonstrated that the mercury complex has different characteristics when compared to L. The TEM, SEM, and powder XRD studies revealed that whereas L is crystalline, that of the mercury complex is not, perhaps a reason for not being able to obtain single crystals of the complex. Binding characteristics of Hg(2+) toward L have been established based on the DFT computational calculations.     

Luminescence behavior of a water soluble calix[4]arene derivative complex with terbium ion(III) in gelation solution

The complexation luminescence behavior of a water soluble calix[4]arene derivative, 5,11,17,23-tetra-sulfonate-25,26,27,28-tetra-carboxymethoxycalix[4]arene (L) with lanthanoid ion (Tb(3+)) has been investigated in gelation solution at 25 degrees C by using UV-vis and fluorescence spectra. The results obtained indicated that the water soluble calix[4]arene derivative can form an efficient energy transfer complex with terbium ion(III). The fluorescence of L x Tb(3+)complex is partially quenched by gelatin in gelation solution. The quenching intensity is related to the concentration and the hydrolysis degree of gelatin. Absorption and fluorescence spectra analysis show that the -COO(-) groups on gelatin have a definite binding ability to Tb(3+), and then, gelatin could compete binding with calix[4]arene derivative upon complexation with Tb(3+), leading to the relative fluorescence quenching of the formation complex of terbium(III) ion with calix[4]arene derivative.     

Alkali and alkaline-earth-metalated forms of calix[4]arenes: synthons in the synthesis of transition metal complexes

This is the first coherent report on the metalation of calix[4]arene by alkali and alkaline-earth metals, thus providing a high-yield production of appropriate synthons for the synthesis of transition metal calix[4]arenes. In addition, various facets of the coordination chemistry by calix[4]arene anions of alkali and alkaline-earth metal ions have been singled out. Among them: 1) the exo and endo coordination of metal ions by the calix[4]arene skeleton; 2) the pi solvation of the ions by the phenyl rings; 3) the ion-carrier properties of metallacalix[4]arenes; 4) the simulation of the kinetically labile coordination sphere of alkali and alkaline-earth metal ions by a polyoxo rigid skeleton. The peculiarities of the complexation of alkali and alkaline-earth metal ions by calix[4]arenes outlined are deduced from the synthesis and the structural characterization both in solution ((1)H NMR) and in the solid state (X-ray structure analysis) of the following classes of compounds: 1) [p-tBu-calix[4](OMS(n))(4)](2) (M=Li, Na, K); 2) [p-tBu-calix[4](OR)(2)(O)(2)ML] (M=Mg, L=THF, R=C(5)H(9); M=Ca, L=TMEDA (tetramethylethylenediamine), R=C(5)H(9); M=Ca, L=DME (dimethoxyethane), R=C(5)H(9); M=Ba, L=TMEDA, R=C(5)H(9); M=Ba, L=none, R=C(5)H(9)); 3) [p-tBu-calix[4](OC(5)H(9))(2)(O)(2)Ca(2)I(2)(MeCN)(2)]; 4) [(p-tBu-calix[4](OR)(2)(O)(2))(2)BaNa(2)].     

Polarizing a hydrophobic cavity for the efficient binding of organic guests: the case of calix[6]tren, a highly efficient and versatile receptor for neutral or cationic species

The host-guest properties of calix[6]tren 1 have been evaluated. The receptor is based on a calix[6]arene that is covalently capped at the narrow rim by a tren unit. As a result, the system presents a concave hydrophobic cavity with, at its bottom, a grid-like nitrogenous core. Despite its well-defined cavity and opening to the outside at the large rim, 1 did not behave as a good receptor for neutral molecules in chloroform. However, it exhibited efficient endo-complexation of ammonium guests. By contrast, the per-protonated host, 1.4H(+), behaved as a remarkable receptor for small organic molecules. The complexation is driven by a strong charge-dipole interaction and hydrogen bonds between the polar guest and the tetracationic cap of the calixarene. Finally, coordination of Zn(2+) to the tren core led to the asymmetrization of calixarene cavity and to the strong but selective endo-binding of neutral ligands. This study emphasizes the efficiency of a receptor presenting a concave hydrophobic cavity that is polarized at its bottom. The resulting combination of charge-dipole, hydrogen bonding, CH-pi, and van der Waals interactions highly stabilizes the supramolecular architectures. Also, importantly, the tren cap allows the tuning of the polarization, offering either a basic (1), a highly charged and acidic (1.4H(+)), or a coordination (1.Zn(2+)) site. As a result, the system proved to be highly versatile, tunable, and interconvertible in solution by simple addition of protons, bases, or metal ions.     

Selective complex formation of some chromogenic calix[4]arene derivatives detected by Fourier transform infrared spectroscopy 1. Solution experiments

A calix[4]arene derivative containing ethoxycarbonylmethoxy groups in the coordination sphere and an iminopyridinium indicator group was studied by FT-IR spectroscopy in acetonitrile solution. The characteristic changes of v(C=O) stretching vibration offered an opportunity for the improvement on selectivity of the ion recognition process of this ligand. The shift of the carbonyl stretching vibration band depended on complex formation as well as on the equilibrium constants of complex formation. In the case of sodium complex, a well-defined isobestic point was detected in the v(C=O) region while altering the sodium concentration. The affinity of thallium(III) to form complex with calixarene 1 was found comparable with those of lithium, sodium or calcium. The complex was found to be an M2L type supramolecule, whereas one molecule of triethylamine was necessary for the formation of each complex.     

Nickel(II) and iron(II) triple helicates assembled from expanded quaterpyridines incorporating flexible linkages

In the present study the interaction of Fe(II) and Ni(II) with the related expanded quaterpyridines, 1,2-, 1,3- and 1,4-bis-(5'-methyl-[2,2']bipyridinyl-5-ylmethoxy)benzene ligands (4-6 respectively), incorporating flexible, bis-aryl/methylene ether linkages in the bridges between the dipyridyl domains, was shown to predominantly result in the assembly of [M(2)L(3)](4+) complexes; although with 4 and 6 there was also evidence for the (minor) formation of the corresponding [M(4)L(6)](8+) species. Overall, this result contrasts with the behaviour of the essentially rigid 'parent' quaterpyridine 1 for which only tetrahedral [M(4)L(6)](8+) cage species were observed when reacted with various Fe(II) salts. It also contrasts with that observed for 2 and 3 incorporating essentially rigid substituted phenylene and biphenylene bridges between the dipyridyl domains where reaction with Fe(II) and Ni(II) yielded both [M(2)L(3)](4+) and [M(4)L(6)](8+) complex types, but in this case it was the latter species that was assigned as the thermodynamically favoured product type. The X-ray structures of the triple helicate complexes [H(2)O?Ni(2)(4)(3)](PF(6))(4)·THF·2.2H(2)O, [Ni(2)(6)(3)](PF(6))(4)·1.95MeCN·1.2THF·1.8H(2)O, and the very unusual triple helicate PF(6)(-) inclusion complex, [(PF(6))?Ni(2)(5)(3)](PF(6))(3)·1.75MeCN·5.25THF·0.25H(2)O are reported.     

Metal complexes with a new N(4)O(3) amine pendant-armed macrocyclic ligand: synthesis, characterization, crystal structures, and fluorescence studies

The synthesis of a new oxaaza macrocyclic ligand, L, derived from O(1),O(7)-bis(2-formylphenyl)-1,4,7-trioxaheptane and tren containing an amine terminal pendant arm, and its metal complexation with alkaline earth (M = Ca(2+), Sr(2+), Ba(2+)), transition (M = Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+)), post-transition (M = Pb(2+)), and Y(3+) and lanthanide (M = La(3+), Er(3+)) metal ions are reported. Crystal structures of [H(2)L](ClO(4))(2).3H(2)O, [PbL](ClO(4))(2), and [ZnLCl](ClO(4)).H(2)O are also reported. In the [PbL] complex, the metal ion is located inside the macrocyclic cavity coordinated by all N(4)O(3) donor atoms while, in the [ZnLCl] complex, the metal ion is encapsulated only by the nitrogen atoms present in the ligand. pi-pi interactions in the [H(2)L](ClO(4))(2).3H(2)O and [PbL](ClO(4))(2) structures are observed. Protonation and Zn(2+), Cd(2+), and Cu(2+) complexation were studied by means of potentiometric, UV-vis, and fluorescent emission measurements. The 10-fold fluorescence emission increase observed in the pH range 7-9 in the presence of Zn(2+) leads to L as a good sensor for this biological metal in water solution.     

Equilibrium studies on complexation in water and solvent extraction of zinc(II) and cadmium(II) with benzo-18-crown-6

The formation constants (K(ML)) in water of 1:1 complexes of benzo-18-crown-6 (B18C6) and 18-crown-6 (18C6) with Zn(2+) and Cd(2+), the sizes of which are much smaller than the ligand cavities, were determined at 25 degrees C by conductometry. Compared with Cd(2+), the crown ethers form more stable complexes with Zn(2+) although the size of Zn(2+) is less suited for the cavities. B18C6 forms a more stable complex with each metal ion than 18C6. Moreover, the extraction equilibria of these metal ions (M(2+)) with B18C6 (L) for the benzene/water system in the presence of picric acid (HA) were investigated at 25 degrees C. The association between L and HA in benzene was examined for evaluating the intrinsic extraction equilibria of M(2+) with B18C6. The extracted species were found to be MLA(2) and ML(2)A(2), and the overall extraction constants (K(ex,1) and K(ex,2), respectively) were obtained. The values of K(ex,1) for these metal ions are almost the same, but the K(ex,2) is larger for Zn(2+) than for Cd(2+). The extraction selectivity was interpreted quantitatively by the constituent equilibrium constants, i.e. K(ML), the ion-pair extraction constant of ML(2+) with A(-), and the adduct formation constant of MLA(2) with L in benzene.     

Supramolecular control of hetero-multinuclear polytopic binding of metal ions (Zn(II), Cu(I)) at a single calix[6]arene-based scaffold

A Calix[6]arene scaffold was functionalized to provide a tridentate binding site at the small rim and three bidentate chelate sites at the large rim of the cone to generate a heteropolytopic ligand. Its complexation to one equivalent of Zn(II) at the small rim yields a funnel complex displaying both host-guest properties and preorganization of the three chelate groups at the large rim. These two aspects allowed the full control of the binding events to regioselectively form dinuclear Zn(II) and heteropolynuclear Zn(II)/Cu(I) complexes. The heteropolynuclear systems all rely on the host-guest relationship thanks to the induced-fit behavior of the calix cavity. With the short guest MeCN, the large rim is preorganized into a trigonal tris-triazole core and accommodates a single Cu(I) ion. A long guest breaks this spatial arrangement, and three Cu(I) ions can then be bound at the tris-bidentate triazole-dimethylamine site at the large rim. In a noncoordinating solvent however, the tetranuclear complex is submitted to scrambling and the addition of exogenous π-acceptor ligands is required to control the binding of Cu(I) in a well-defined environment. Hindrance selectivity was then induced by the accessibility at the small rim site. Indeed, while CO can stabilize Cu(I) at both coordination sites, PPh(3) cannot fit into the cavity and forces Cu(I) to relocate at the large rim. The resulting well-defined symmetrical tetranuclear complex thus arises from the quite remarkable selective supramolecular assembly of nine partners (1 Zn(II), 3 Cu(I), 1 calixarene, 1 guest alkylamine, 3 PPh(3)).     

Phenoxyl radicals: H-bonded and coordinated to Cu(II) and Zn(II)

Two pro-ligands ((R)LH) comprised of an o,p-di-tert-butyl-substituted phenol covalently bonded to a benzimidazole ((Bz)LH) or a 4,5-di-p-methoxyphenyl substituted imidazole ((PhOMe)LH), have been structurally characterised. Each possesses an intramolecular O-H[dot dot dot]N hydrogen bond between the phenolic O-H group and an imidazole nitrogen atom and (1)H NMR studies show that this bond is retained in solution. Each (R)LH undergoes an electrochemically reversible, one-electron, oxidation to form the [(R)LH] (+) radical cation that is considered to be stabilised by an intramolecular O...H-N hydrogen bond. The (R)LH pro-ligands react with M(BF(4))(2).H(2)O (M = Cu or Zn) in the presence of Et(3)N to form the corresponding [M((R)L)(2)] compound. [Cu((Bz)L)(2)] (), [Cu((PhOMe)L)(2)] (), [Zn((Bz)L)(2)] and [Zn((PhOMe)L)(2)] have been isolated and the structures of .4MeCN, .2MeOH, .2MeCN and .2MeCN determined by X-ray crystallography. In each compound the metal possesses an N(2)O(2)-coordination sphere: in .4MeCN and .2MeOH the {CuN(2)O(2)} centre has a distorted square planar geometry; in .2MeCN and .2MeCN the {ZnN(2)O(2)} centre has a distorted tetrahedral geometry. The X-band EPR spectra of both and , in CH(2)Cl(2)-DMF (9 : 1) solution at 77 K, are consistent with the presence of a Cu(ii) complex having the structure identified by X-ray crystallography. Electrochemical studies have shown that each undergo two, one-electron, oxidations; the potentials of these processes and the UV/vis and EPR properties of the products indicate that each oxidation is ligand-based. The first oxidation produces [M(II)((R)L)((R)L )](+), comprising a M(ii) centre bound to a phenoxide ((R)L) and a phenoxyl radical ((R)L ) ligand; these cations have been generated electrochemically and, for R = PhOMe, chemically by oxidation with Ag[BF(4)]. The second oxidation produces [M(II)((R)L )(2)](2+). The information obtained from these investigations shows that a suitable pro-ligand design allows a relatively inert phenoxyl radical to be generated, stabilised by either a hydrogen bond, as in [(R)LH] (+) (R = Bz or PhOMe), or by coordination to a metal, as in [M(II)((R)L)((R)L )](+) (M = Cu or Zn; R = Bz or PhOMe). Coordination to a metal is more effective than hydrogen bonding in stabilising a phenoxyl radical and Cu(ii) is slightly more effective than Zn(II) in this respect.     

Synthesis and structures of an unusual germanium(II) calix[4]arene complex and the first germanium(II) calix[8]arene complex and their reactivity with diiron nonacarbonyl

The protonolysis reaction of the germanium(II) amide Ge[N(SiMe3)2]2 with calix[4]arene and calix[8]arene furnishes the two germanium(II) calixarene complexes {calix[4]}Ge2 and {calix[8]}Ge4, respectively, which have been crystallographically characterized. The calix[4]arene complex contains a Ge2O2 rhombus at the center of the molecule and is one of the only four germanium(II) calix[4]arenes that have been structurally characterized. The calix[8]arene species is the first reported germanium calix[8]arene complex, and it exhibits an overall bowl-shaped structure which contains two Ge2O2 fragments. The latter complex reacts with Fe2(CO)9 to yield an octairon compound, which has also been structurally characterized and contains four GeFe2 triangles arranged around the macrocyclic ring. The germanium(II) centers are oxidized to germanium(IV) in this process, with concomitant reduction of the neutral diiron species to Fe2(CO)(8)2- anions.     

Coordination chemistry of a new cofacial binucleating macropolycycle derived from 1,4,7-triazacyclononane

We have prepared and characterized a new phenol-based compartmental ligand (H(2)L) incorporating 1,4,7-triazacyclononane ([9]aneN(3)), and we have investigated its coordination behavior with Cu(II), Zn(II), Cd(II), and Pb(II). The protonation constants of the ligand and the thermodynamic stabilities of the 1:1 and 2:1 (metal/ligand) complexes with these metal ions have been investigated by means of potentiometric measurements in aqueous solutions. The mononuclear [M(L)] complexes show remarkably high stability suggesting that, along with the large number of nitrogen donors available for metal binding, deprotonated phenolic functions are also involved in binding the metal ion. The mononuclear complexes [M(L)] show a marked tendency to add a second metal ion to afford binuclear species. The formation of complexes [M(2)(H(2)L)](4+) occurs at neutral or slightly acidic pH and is generally followed by metal-assisted deprotonation of the phenolic groups to give [M(2)(HL)](3+) and [M(2)(L)](2+) in weakly basic solutions. The complexation properties of H(2)L have also been investigated in the solid state. Crystals suitable for X-ray structural analysis were obtained for the binuclear complexes [Cu(2)(L)](BF(4))(2).(1)/(2)MeCN (1), [Zn(2)(HL)](ClO(4))(3).(1)/(2)MeCN (2), and [Pb(2)(L)](ClO(4))(2).2MeCN (4). In 1 and 2, the phenolate O-donors do not bridge the two metal centers, which are, therefore, segregated each within an N(5)O-donor compartment. However, in the case of the binuclear complex [Pb(2)(L)](ClO(4))(2).2MeCN (4), the two Pb(II) centers are bridged by the phenolate oxygen atoms with each metal ion sited within an N(5)O(2)-donor compartment of L(2)(-), with a Pb.Pb distance of 3.9427(5) A.