Four-coordinate Structure Research Articles

Hydrogen-bond-reversal symmetry and its violation in ice nanotubes

Recently, a new type of generalized symmetry of ice structures was introduced which takes into account the change of direction of all hydrogen bonds. The energy nonequivalence of pairs of configurations with opposite direction of all hydrogen bonds was established in the course of computer simulation of bilayer ice and other four-coordinated structures without `dangling' hydrogen atoms. In this article, the results of detailed investigations of the violation of the hydrogen-bond-reversal symmetry in ice nanotubes consisting of stacked n-membered rings are presented. A comprehensive classification of all possible hydrogen-bonding configurations and their division into two classes (antisymmetrical and non-antisymmetrical) are given. Attention is focused on the most stable configurations that have no longitudinally arranged water molecules. This restriction made the asymmetry very difficult to find. For example, it was established that the asymmetry (non-antisymmetrical configurations) in ice nanotubes with square, pentagonal and hexagonal cross sections appears only when the number of transverse rings in the unit cell is more than six. It is shown that this is related to the well known combinatorial problem of enumerating the symmetry-distinct necklaces of black and white beads. It was found that, among the ice nanotubes that had been considered, hydrogen-bond-reversal asymmetry is most conspicuous in wide nanotubes such as heptagonal and octagonal. In this case the asymmetry is observed for unit cells of any length. In order to verify the results of the symmetry analysis and to confirm the energy nonequivalence of some (non-antisymmetrical) configurations, approximate calculations of the binding energy have been performed using the package TINKER.

Spectral studies of transition metal complexes of dihydrobis(1-pyrazoyl)borate with some Lewis bases

Co(II), Ni(II) and Cu(II) complexes of dihydrobis(1-pyrazolyl)borate and their adducts with some Lewis bases have been prepared and characterized by elemental analyses, IR and UV–vis spectroscopic techniques. The adducts were either 1:1 or 1:2 complexes depending on whether the Lewis base was bidentate or monodentate. The results indicate that adducts with 1,10-phenanthroline were the most stable due to the chelating effect of the Lewis base. The order of reactivity of the complexes was determined to be Ni(H2BPz2)2>Cu(H2BPz2)2>CoH2(BPz2)2>Co(H2BPz2)2. The effects of various solvents (i.e., benzene, chloroform and DMF) on the structure were studied. The solvents appear to minimally affect the visible spectra of Co(H2BPz2)2. The Ni(H2BPz2)2 and Cu(H2BPz2)2 adducts exhibit a four-coordinate structure in non-coordinating solvents. However, in coordinating solvents, such as DMF, the adducts exhibit six-coordinate structures.

A comparative study of cytotoxicity and interaction with DNA/protein of five transition metal complexes with Schiff base ligands

Five transition metal complexes NiL12 (1), CuL12 (2), ZnL12 (3), [MnL12(N3)]n·nCH2Cl2 (4), CuL22 (5) {HL1=3-{[2-(2-hydroxy-ethoxy)-ethylimino]-methyl}-naphthalen-2-ol, HL2=2-{[2-(2-hydroxy-ethoxy)-ethylimino]-methyl}-phenol} have been synthesized and fully characterized. In all of the complexes, the ligands coordinated to the metal ion in a negative fashion via O and N donor atoms. The X-ray structures of nickel complex 1 and copper complexes 2 and 5 are four-coordinated monomers and show slightly distorted square-planar geometry in the vicinity of the central metal atom. Zinc complex 3 exhibits a four-coordinated tetrahedral structure. Differently, manganese complex 4 reveals a six-coordinated octahedral structure, one-dimensional chain is linked by azide in the end-to-end mode. In vitro cytotoxicity of these complexes to various tumor cell lines was assayed by the MTT method. The results showed that most of these metal-Schiff base complexes exhibited enhanced cytotoxicity than Schiff base ligands, which clearly implied a positive synergistic effect. Moreover, these complexes appeared to be selectively active against certain cell lines. The interactions of these metal complexes with CT-DNA were investigated by UV–vis, fluorescence and CD spectroscopy, the results indicated that these complexes are metallointercalators and can interact with CT-DNA. The study of interaction between complexes and BSA indicated that all of the complexes could quench the intrinsic fluorescence of BSA in a static quenching process.

Syntheses and characterizations of two new energetic copper–amine-DNANT complexes and their effects on thermal decomposition of RDX

Abstract Two novel copper complexes of dinitroacetonitrile (DNANT), Cu(NH3)4(DNANT)2 (1) and Cu(en)2(DNATN)2 (2), have been synthesized for the first time through an unique reaction, and structurally characterized. The single-crystal X-ray structural analysis shows that the Cu2+ cations in the two complexes share a similar four-coordinated structure, which however does not directly involve the main energetic DNANT− anion. The differential scanning calorimetry (DSC) study reveals that the two complexes have higher thermal stability and lower sensitivity than the analogous FOX-7 complexes, and exhibit good catalytic action to the decomposition of RDX.

Sugar complexation to silicone boronic acids

A new class of surface-active compounds based on the combination of silicones and boronic acids is described. The properties of the compounds can be tuned by manipulation of both the hydrophobic (silicone size and 3D structure) and hydrophilic components (by binding different saccharides to the boronic acid). Stabilization of the four-coordinate boron structure is provided by Tris buffer that also maintains neutral pH to suppress silicone hydrolysis.

A study on phase transformation of monocrystalline silicon due to ultra-precision polishing by molecular dynamics simulation

A three-dimensional molecular dynamics (MD) simulation is conducted to investigate the material removal mechanism of monocrystalline silicon by mechanical polishing at atomistic scale with diamond abrasives. By monitoring relative positions of atoms in the monocrystalline silicon specimen, the microstructure transformation of monocrystalline silicon is clearly identified and analyzed. The phase transformation is accomplished under extreme conditions with high temperature and huge hydrostatic pressure, and as a result the silicon microstructure transforms from the four-coordinated diamond cubic structure (Si-I) to the six-coordinated body-centered tetragonal structure (β-silicon). The values of local pressure and temperature are consistent with previous experimental results. In addition, the force between the diamond abrasive and specimen indicates the occurrence of phase transformation in the specimen. The potential energy of each atom is also calculated, which provides us an effective approach to analyze the energy variation of atoms in the mechanism of material deformation and the formation of machined surface after ultra-precision polishing.

Quadruply bonded dimolybdenum complexes with highly unusual geometries and vacant coordination sites

New quadruply bonded dimolybdenum complexes of the terphenyl ligand Ar(Xyl(2)) (Ar(Xyl(2)) = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) have been prepared and structurally characterized. The steric hindrance exerted by the Ar(Xyl(2)) groups causes the Mo atoms to feature unsaturated four-coordinate structures and a formal fourteen-electron count.

Bis[μ3-N′-oxidopyridine-2-carboximidamidato(2−)]bis[μ2-N′-oxidopyridine-2-carboximidamidato(1−)]tetrapyridinetetranickel(II) dinitrate

The title compound, [Ni4(C6H5N3O)2(C6H6N3O)2(C5H5N)4](NO3)2, is a tetra­nuclear nickel complex containing a single-decker cation, located on an inversion center. The two unique NiII cations are N,N′,N′′,O-chelated by carbox­imid­amid­ate(2−) and carboximidamidate(1−) anions, forming a distorted four-coordinate planar structure, while the other two NiII atoms are N,N′,O,O′-chelated by the same bridging ligands and two pyridine mol­ecules, affording six-coordinated metals in an octa­hedral geometry. The cation is isostructural with the complex crystallized with perchlorate counter-ions in place of nitrate.

Formation of Nanocolloidal Metacinnabar in Mercury-DOM-Sulfide Systems

Direct determination of mercury (Hg) speciation in sulfide-containing environments is confounded by low mercury concentrations and poor analytical sensitivity. Here we report the results of experiments designed to assess mercury speciation at environmentally relevant ratios of mercury to dissolved organic matter (DOM) (i.e., <4 nmol Hg (mg DOM)(-1)) by combining solid phase extraction using C(18) resin with extended X-ray absorption fine structure (EXAFS) spectroscopy. Aqueous Hg(II) and a DOM isolate were equilibrated in the presence and absence of 100 μM total sulfide. In the absence of sulfide, mercury adsorption to the resin increased as the Hg:DOM ratio decreased and as the strength of Hg-DOM binding increased. EXAFS analysis indicated that in the absence of sulfide, mercury bonds with an average of 2.4 ± 0.2 sulfur atoms with a bond length typical of mercury-organic thiol ligands (2.35 Å). In the presence of sulfide, mercury showed greater affinity for the C(18) resin, and its chromatographic behavior was independent of Hg:DOM ratio. EXAFS analysis showed mercury-sulfur bonds with a longer interatomic distance (2.51-2.53 Å) similar to the mercury-sulfur bond distance in metacinnabar (2.53 Å) regardless of the Hg:DOM ratio. For all samples containing sulfide, the sulfur coordination number was below the ideal four-coordinate structure of metacinnabar. At a low Hg:DOM ratio where strong binding DOM sites may control mercury speciation (1.9 nmol mg(-1)) mercury was coordinated by 2.3 ± 0.2 sulfur atoms, and the coordination number rose with increasing Hg:DOM ratio. The less-than-ideal coordination numbers indicate metacinnabar-like species on the nanometer scale, and the positive correlation between Hg:DOM ratio and sulfur coordination number suggests progressively increasing particle size or crystalline order with increasing abundance of mercury with respect to DOM. In DOM-containing sulfidic systems nanocolloidal metacinnabar-like species may form, and these species need to be considered when addressing mercury biogeochemistry.

Accurate Fabrication of Hydroxyapatite Bone Models with Porous Scaffold Structures by Using Stereolithography

Computer graphic models of bioscaffolds with four-coordinate lattice structures of solid rods in artificial bones were designed by using a computer aided design. The scaffold models composed of acryl resin with hydroxyapatite particles at 45vol. % were fabricated by using stereolithography of a computer aided manufacturing. After dewaxing and sintering heat treatment processes, the ceramics scaffold models with four-coordinate lattices and fine hydroxyapatite microstructures were obtained successfully. By using a computer aided analysis, it was found that bio-fluids could flow extensively inside the sintered scaffolds. This result shows that the lattice structures will realize appropriate bio-fluid circulations and promote regenerations of new bones.

A structural study of Cu–In–Se compounds by x-ray absorption fine structure

Abstract

CuCl3]− and [CuCl4]2− Hydrates in Concentrated Aqueous Solution: A Density Functional Theory and ab Initio Study

In this work, structures and thermodynamic properties of [CuCl(3)](-) and [CuCl(4)](2-) hydrates in aqueous solution were investigated using density functional theory and ab initio methods. Contact ion pair (CIP) and solvent-shared ion pair (SSIP) structures were both taken into account. Our calculations suggest that [CuCl(3)(H(2)O)(n)](-) clusters might favor a four-coordinated CIP structure with a water molecule coordinating with the copper atom in the equatorial position for n = 3 and 4 in aqueous solution, whereas the four-coordinated SSIP structure with one chloride atom dissociated becomes more stable as n increases to 5. For the [CuCl(4)](2-) cluster, the four-coordinated tetrahedron structure is more stable than the square-planar one, whereas for [CuCl(4)(H(2)O)(n)](2-) (n ≥ 1) clusters, it seems that four-coordinated SSIP structures are slightly more favorable than CIP structures. Our calculations suggest that Cu(2+) perhaps prefers a coordination number of 4 in CuCl(2) aqueous solution with high Cl(-) concentrations. In addition, natural bond orbital (NBO) calculations suggest that there is obvious charge transfer (CT) between copper and chloride atoms in [CuCl(x)](2-x) (x = 1-4) clusters. However, compared with that in the [CuCl(2)](0) cluster, the CT between the copper and chloride atoms in [CuCl(3)](-) and [CuCl(4)](2-) clusters becomes negligible as the number of attached redundant Cl(-) ions increases. This implies that the coordination ability of Cl(-) is greatly weakened for [CuCl(3)](-) and [CuCl(4)](2-) clusters. Electronic absorption spectra of these different hydrates were obtained using long-range-corrected time-dependent density functional theory. The calculated electronic transition bands of the four-coordinated CIP conformer of [CuCl(3)(H(2)O)(n)](-) for n = 3 and 4 are coincident with the absorption of [CuCl(3)](-)(aq) species (∼284 and 384 nm) resolved from UV spectra obtained in CuCl(2) (ca. 10(-4) mol·kg(-1)) + LiCl (>10 mol·kg(-1)) solutions, whereas the calculated bands of [CuCl(3)(H(2)O)(n)](-) in their most stable configurations are not when n = 0 - 2 or n > 4, which means that the species [CuCl(3)](-)(aq) exists in those CuCl(2) aqueous solutions in which the water activity is neither too low nor too high. The calculated bands of [CuCl(4)(H(2)O)(n)](2-) clusters correspond to the absorption spectra (∼270 and 370 nm) derived from UV measurements only when n = 0, which suggests that [CuCl(4)](2-)(aq) species probably exist in environments in which the water activity is quite low.

CO and O2 Binding to Pseudo-tetradentate Ligand−Copper(I) Complexes with a Variable N-Donor Moiety: Kinetic/Thermodynamic Investigation Reveals Ligand-Induced Changes in Reaction Mechanism

The kinetics, thermodynamics, and coordination dynamics are reported for O(2) and CO 1:1 binding to a series of pseudo-tetradentate ligand-copper(I) complexes ((D)LCu(I)) to give Cu(I)/O(2) and Cu(I)/CO product species. Members of the (D)LCu(I) series possess an identical tridentate core structure where the cuprous ion binds to the bispicolylamine (L) fragment. (D)L also contains a fourth variable N-donor moiety {D = benzyl (Bz); pyridyl (Py); imidazolyl (Im); dimethylamino (NMe(2)); (tert-butylphenyl)pyridyl (TBP); quinolyl (Q)}. The structural characteristics of (D)LCu(I)-CO and (D)LCu(I) are detailed, with X-ray crystal structures reported for (TBP)LCu(I)-CO, (Bz)LCu(I)-CO, and (Q)LCu(I). Infrared studies (solution and solid-state) confirm that (D)LCu(I)-CO possess the same four-coordinate core structure in solution with the variable D moiety "dangling", i.e., not coordinated to the copper(I) ion. Other trends observed for the present series appear to derive from the degree to which the D-group interacts with the cuprous ion center. Electrochemical studies reveal close similarities of behavior for (Im)LCu(I) and (NMe(2))LCu(I) (as well as for (TBP)LCu(I) and (Q)LCu(I)), which relate to the O(2) binding kinetics and thermodynamics. Equilibrium CO binding data (K(CO), ΔH°, ΔS°) were obtained by conducting UV-visible spectrophotometric CO titrations, while CO binding kinetics and thermodynamics (k(CO), ΔH(double dagger), ΔS(double dagger)) were measured through variable-temperature (193-293 K) transient absorbance laser flash photolysis experiments, λ(ex) = 355 nm. Carbon monoxide dissociation rate constants (k(-CO)) and corresponding activation parameters (ΔH(double dagger), ΔS(double dagger)) have also been obtained. CO binding to (D)LCu(I) follows an associative mechanism, with the increased donation from D leading to higher k(CO) values. Unlike observations from previous work, the K(CO) values increased as the k(CO) and k(-CO) values declined; the latter decreased at a faster rate. By using the "flash-and-trap" method (λ(ex) = 355 nm, 188-218 K), the kinetics and thermodynamics (k(O(2)), ΔH(double dagger), ΔS(double dagger)) for O(2) binding to (NMe(2))LCu(I) and (Im)LCu(I) were measured and compared to those for (Py)LCu(I). A surprising change in the O(2) binding mechanism was deduced from the thermodynamic ΔS(double dagger) values observed, associative for (Py)LCu(I) but dissociative for (NMe(2))LCu(I) and (Im)LCu(I); these results are interpreted as arising from a difference in the timing of electron transfer from copper(I) to O(2) as this molecule coordinates and a tetrahydrofuran (THF) solvent molecule dissociates. The change in mechanism was not simply related to alterations in (D)LCu(II/I) geometries or the order in which O(2) and THF coordinate. The equilibrium O(2) binding constant (K(O(2)), ΔH°, ΔS°) and O(2) dissociation rate constants (k(-O(2)), ΔH(double dagger), ΔS(double dagger)) were also determined. Overall the results demonstrate that subtle changes in the coordination environment, as occur over time through evolution in nature or through controlled ligand design in synthetic systems, dictate to a critically detailed level the observed chemistry in terms of reaction kinetics, structure, and reactivity, and thus function. Results reported here are also compared to relevant copper and/or iron biological systems and analogous synthetic ligand-copper systems.

Hydrates of Cu2+ and CuCl+ in Dilute Aqueous Solution: A Density Functional Theory and Polarized Continuum Model Investigation

In this work, structures, and properties of Cu(2+) and CuCl(+) hydrates in the gas and aqueous phases have been investigated using the B3LYP method. Contact ion pair (CIP) and solvent-shared ion pair (SSIP) were both taken into account for CuCl(+) hydrates. Our calculations show that [Cu(H(2)O)(n)](2+) clusters favor a very open four-coordinated structure for n = 5-12 in the gas phase, while a five-coordinated conformer is favored for n > or = 8 in the aqueous phase. An approximate complete solvation shell of Cu(2+) in the aqueous phase needs more than 12 water molecules, while that of CuCl(+) in the aqueous phase needs only about eight water molecules. For [CuCl(H(2)O)(n)](+) clusters, the most stable structure is a four-coordinated CIP conformer for n = 4-7 in the gas phase and a five-coordinated CIP conformer for n = 8-10 in the aqueous phase. However, the five-coordinated CIP/h conformer (CIP conformer that the axial chloride atom tends to dissociate) of [CuCl(H(2)O)(n)](+) clusters becomes more favorable as n increases to 11. As the hydration process proceeds, the charges on the copper atom of [Cu(H(2)O)(n)](2+) clusters decrease, while those of [CuCl(H(2)O)(n)](+) clusters increase (probably due to the dissociation of Cl(-)). The d-d electron transition and partial charge transition band around 160 nm of the five-coordinated conformer of [Cu(H(2)O)(n)](2+) clusters and those bands (approximately 170 and approximately 160 nm) of SSIP or five-coordinated CIP/h conformers of [CuCl(H(2)O)(n)](+) clusters are coincident with the absorption of [Cu](2+)(aq) species (approximately 180 nm) resolved from the spectra obtained in trace CuCl(2) (ca. 10(-5) mol x kg(-1)) + LiCl (0-18 mol x kg(-1)) aqueous solution, while those of five-coordinated CIP conformers of [CuCl(H(2)O)(n)](+) clusters (n = 8 and 9) around 261 and 247 nm correspond to the absorption of [CuCl](+)(aq) species (approximately 250 nm). Our calculated electronic spectra indicate that the typical peak of copper(II)-chloride complexes changes from 180 to 250 nm, and 275 nm, as the process of Cl(-) coordination. For [Cu](2+)(aq), [CuCl](+)(aq), and [CuCl(2)](0)(aq) species, the central Cu(II) atom prefers five-coordination.

Steric Crowding Effect of 1,3-Diketonates on the Structures and the Solution Behaviors of Nickel(II) Mixed-Ligand Complexes

Abstract Seven nickel(II) mixed-ligand complexes were synthesized: Ni(dike)(diam)X, where dike is a 1,3-diketonate such as 3,5-heptanedionate (dedk) or 2,6-dimethyl-3,5-heptanedionate (dmhd), diam is an N-alkylated ethylenediamine such as N,N,N′,N′-tetramethylethylenediamine (tmen) or 1,2-dipiperidinoethane (dipe), and X is BPh4− or NO3−. The crystal structures were analyzed: each nitrate complex has a six-coordinated octahedral structure with a bidentate-coordinated nitrate, and each tetraphenylborate complex has a four-coordinated square-planar structure. The ligand field strength of [Ni(dike)(diam)]BPh4 in the solid state increases in the order: [Ni(dmhd)(dipe)]BPh4 &amp;lt; [Ni(dedk)(dipe)]BPh4 &amp;lt; [Ni(dmhd)(tmen)]BPh4 = [Ni(dedk)(tmen)]BPh4. In solution, the change of the color depending on the donor/acceptor ability of the solvent, i.e., solvatochromism was observed. When dimethyl sulfoxide was added to a solution of [Ni(dike)(diam)]BPh4 in inert 1,2-dichloroethane, the adduct formation constants are in the order: [Ni(dmhd)(dipe)]BPh4 &amp;lt; [Ni(dedk)(dipe)]BPh4 &amp;lt;&amp;lt; [Ni(dmhd)(tmen)]BPh4 = [Ni(dedk)(tmen)]BPh4, reflecting the difference in steric hindrance of the ligands rather than the difference in ligand field strength. The steric crowding effect of 1,3-diketonates was observed in the solid state and solution when bulky dipe is used as diamine.

Catalysis of the Suzuki–Miyaura coupling reaction in water by heteroannular cyclopalladated ferrocenylimine complexes

Catalytic studies on the air- and moisture-stable triphenylphosphine (PPh3) adducts of heteroannular cyclopalladated ferrocenylimines [PdCl{C5H4FeC5H4CHRN=CHC4H3X}(Ph3P)] (R = H, CH3; X = S, O) indicate that they are all effective catalysts for the Suzuki–Miyaura coupling reaction of activated aryl bromides with phenylboronic acid in water under air atmosphere. Typically, using 1 mol‰ of catalyst in the presence of 1.2 equivalents of K3PO4 as base in water at 100 °C provided the corresponding biaryls in good to excellent yields. Meanwhile, the structure of [PdCl{C5H4FeC5H4CH(CH3)N=CHC4H3S}(PPh3)] has been established by the single-crystal X-ray diffraction technique. According to the crystal structure, the palladium atom is bound to the unsubstituted Cp ring, showing the four-coordinate structure typical of palladium complexes.

Synthesis and Characterization of High-silica SAPO-5 from Metakolin

High-silica silicoaluminophosphate(SAPO-5) molecular sieves were hydrothermally synthesized using metakaoline with a certain activity as the silicon and aluminum sources,phosphoric acid as the phosphorus source and triethanolamine combined with cetyltrimethylammonium bromide(CTMABr) as the template agents.The sample was characterized by means of X-ray diffraction spectroscope(XRD),Infrared spectrum(IR),scanning electron microscope(SEM) and 29Si,27Al MAS-NMR and X-ray photoelectron spectroscope(XPS),temperature-programmed desorption of adsorbed NH3.The results show that the crystallization of the SAPO-5 can be promoted by the addition of CTMABr.The synthesized SAPO-5 reveals pillar-like morphology with dimension of 20μm×5μm×5μm.The local environment of Si and Al changs greatly after reaction and many four-coordinated structures such as Al(OP)4 and Si(AlO)4 are produced with the Si/Al ratio of 0.56.The acidity amount of the product is 0.578mmol/g and the ratio of the strong acid sites to the weak acid sites is 0.684.

Infrared and Raman Spectroscopic Studies on Alkali Borate Glasses: Evidence of Mixed Alkali Effect

A lithium-potassium-borate glass system containing manganese and iron cations has been thoroughly investigated in order to obtain information about the mixed alkali effect and the structural role of both the manganese and iron in such glass hosts. Mixed alkali borate glasses of the (30 - x)Li(2)O - xK(2)O - 10CdO/ZnO - 59B(2)O(3) (x = 0, 10, 15, 20, and 30) doped with 1MnO(2)/1Fe(2)O(3) system were prepared by a melt quench technique. The amorphous phase of the prepared glass samples was confirmed from their X-ray diffraction. The spectroscopic properties of glass samples were studied using infrared (IR) and Raman spectroscopic techniques. The density of all the prepared glasses was measured using Archimedes principle. Molar volumes were estimated from the density data. IR spectra of these glasses revealed a dramatic variation of three- and four-coordinated boron structures as a function of mixed alkali concentration. The vibrations due to Li-O, K-O, and MnO(4)/FeO(4) arrangements are consistent in all the compositions and show a nonlinear variation in the intensity with alkali content. Raman spectra of different alkali combinations with CdO and ZnO present drastic changes in the intensity of various Raman bands. The observation of disappearance and reappearance of IR and Raman bands as a function of various alkali concentrations is an important result pertaining to the mixed alkali effect in borate glasses. Acting as complementary spectroscopic techniques, both types of measurements, IR and Raman, revealed that the network structure of the studied glasses is mainly based on BO(3) and BO(4) units placed in different structural groups, the BO(3) units being dominant. The measured IR and Raman spectra of different glasses are used to clarify the optical properties of the present glasses correlating them with their structure and composition.

Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model

The hydrated structure of the Cu(II) ion has been a subject of ongoing debate in the literature. In this article, we use density functional theory (B3LYP) and the COSMO continuum solvent model to characterize the structure and stability of [Cu(H2O)n](2+) clusters as a function of coordination number (4, 5, and 6) and cluster size (n = 4-18). We find that the most thermodynamically favored Cu(II) complexes in the gas phase have a very open four-coordinate structure. They are formed from a stable square-planar [Cu(H2O)8](2+) core stabilized by an unpaired electron in the Cu(II) ion d(x(2)-y(2)) orbital. This is consistent with cluster geometries suggested by recent mass-spectrometric experiments. In the aqueous phase, we find that the more compact five-coordinate square-pyramidal geometry is more stable than either the four-coordinate or six-coordinate clusters in agreement with recent combined EXAFS and XANES studies of aqueous solutions of Cu(II). However, a small energetic difference (approximately 1.4 kcal/mol) between the five- and six-coordinate models with two full hydration shells around the metal ion suggests that both forms may coexist in solution.

Theoretical Study of Hydrated Copper(II) Interactions with Guanine: A Computational Density Functional Theory Study

Optimization of the hydrated Cu(II)(N7-guanine) structures revealed a number of minima on the potential energy surface. For selected structures, energy decompositions together with the determination of electronic properties (partial charges and electron spin densities) were performed. In the complexes of guanine with the bare copper cation and that with the monoaqua ligated cation, an electron transfer from guanine to Cu(II) was observed, resulting in a Cu(I)-guanine(+) type of complex. Conformers with two aqua ligands are borderline systems characterized by a Cu partial charge of +0.7e and a similar value of the spin density (0.6e) localized on guanine. When tetracoordination of copper was achieved, only then the prevailing electron spin density is unambiguously localized on copper. The energetic preference of diaqua-Cu-(N7,O6-guanine) over triaqua-Cu-(N7-guanine) was found for the four-coordinate structures. However, the energy difference between these two conformations decreases with the number of water molecules present in the systems, and in complexes with five water molecules this preference is preserved only at DeltaG level where thermal and entropy terms are included.