A very rare hydrogen-bridged hexanuclear CuII complex containing a triangular Cu3O core capped by an unusual triply coordinated perchlorate anion

An unusual hexanuclear Cu-II complex, [{[Cu(NHDEPO)](3)(mu(3)-O)(O3ClO)}(2)(mu-H)]center dot 7ClO(4)center dot 4H(2)O (1) was prepared starting from Cu(ClO4)(2)center dot 6H(2)O and the oxime-based Schiff base ligand NHDEPO (= 3-[3-(diethylamino)propylimino]butan-2-one oxime). Structural characterization of the complex reveals that it consists of two triangular Cu3O units, the copper ions being at the corners of an equilateral triangle, separated by an O center dot center dot center dot O distance of 2,447(5) angstrom, held together solely by a proton. In each triangle, the copper atoms are in square-pyramid environments. The equatorial plane consists of the bridging oxygen of the central OH-(O2-) group together with three atoms (N, N, O) of the Schiff base. All Unusual triply coordinated perchlorate ion (mu(3)-kappa O:kappa O':kappa O '') interacts in axial position with the three copper ions, Variable-temperature (2-300 K) magnetic susceptibility measurements show that complex 1 is antiferromagnetically Coupled (J = -148 cm(1-)). The EPR data at low temperature clearly indicates the presence of spin frustration phenomenon in the complex.

The influence of carbon surface oxygen groups on Dubinin–Astakhov equation parameters calculated from CO2 adsorption isotherm

We present the results of a systematic study of the influence of carbon surface oxidation on Dubinin–Astakhov isotherm parameters obtained from the fitting of CO2 adsorption data. Using GCMC simulations of adsorption on realistic VPC models differing in porosity and containing the most frequently occurring carbon surface functionalities (carboxyls, hydroxyls and carbonyls) and their mixtures, it is concluded that the maximum adsorption calculated from the DA model is not strongly affected by the presence of oxygen groups. Unfortunately, the same cannot be said of the remaining two parameters of this model i.e. the heterogeneity parameter (n) and the characteristic energy of adsorption (E0). Since from the latter the pore diameters of carbons are usually calculated, by inverse-type relationships, it is concluded that they are questionable for carbons containing surface oxides, especially carboxyls.

The influence of the carbon surface chemical composition on Dubinin-Astakhov equation parameters calculated from SF(6) adsorption data-grand canonical Monte Carlo simulation

Using grand canonical Monte Carlo simulation we show, for the first time, the influence of the carbon porosity and surface oxidation on the parameters of the Dubinin-Astakhov (DA) adsorption isotherm equation. We conclude that upon carbon surface oxidation, the adsorption decreases for all carbons studied. Moreover, the parameters of the DA model depend on the number of surface oxygen groups. That is why in the case of carbons containing surface polar groups, SF(6) adsorption isotherm data cannot be used for characterization of the porosity.

Simple model of adsorption on external surface of carbon nanotubes: a new analytical approach basing on molecular simulation data

Nitrogen adsorption on carbon nanotubes is wide- ly studied because nitrogen adsorption isotherm measurement is a standard method applied for porosity characterization. A further reason is that carbon nanotubes are potential adsorbents for separation of nitrogen from oxygen in air. The study presented here describes the results of GCMC simulations of nitrogen (three site model) adsorption on single and multi walled closed nanotubes. The results obtained are described by a new adsorption isotherm model proposed in this study. The model can be treated as the tube analogue of the GAB isotherm taking into account the lateral adsorbate-adsorbate interactions. We show that the model describes the simulated data satisfactorily. Next this new approach is applied for a description of experimental data measured on different commercially available (and characterized using HRTEM) carbon nanotubes. We show that generally a quite good fit is observed and therefore it is suggested that the observed mechanism of adsorption in the studied materials is mainly determined by adsorption on tubes separated at large distances, so the tubes behave almost independently.

Molecular dynamics simulation insight into the mechanism of phenol adsorption at low coverages from aqueous solutions on microporous carbons

MD simulation studies showing the influence of porosity and carbon surface oxidation on phenol adsorption from aqueous solutions on carbons are reported. Based on a realistic model of activated carbon, three carbon structures with gradually changed microporosity were created. Next, a different number of surface oxygen groups was introduced. The pores with diameters around 0.6 nm are optimal for phenol adsorption and after the introduction of surface oxygen functionalities, adsorption of phenol decreases (in accordance with experimental data) for all studied models. This decrease is caused by a pore blocking effect due to the saturation of surface oxygen groups by highly hydrogen-bounded water molecules.

Can carbon surface oxidation shift the pore size distribution curve calculated from Ar, N(2) and CO(2) adsorption isotherms? Simulation results for a realistic carbon model

Using the virtual porous carbon model proposed by Harris et al, we study the effect of carbon surface oxidation on the pore size distribution (PSD) curve determined from simulated Ar, N(2) and CO(2) isotherms. It is assumed that surface oxidation is not destructive for the carbon skeleton, and that all pores are accessible for studied molecules (i.e., only the effect of the change of surface chemical composition is studied). The results obtained show two important things, i.e., oxidation of the carbon surface very slightly changes the absolute porosity (calculated from the geometric method of Bhattacharya and Gubbins (BG)); however, PSD curves calculated from simulated isotherms are to a greater or lesser extent affected by the presence of surface oxides. The most reliable results are obtained from Ar adsorption data. Not only is adsorption of this adsorbate practically independent from the presence of surface oxides, but, more importantly, for this molecule one can apply the slit-like model of pores as the first approach to recover the average pore diameter of a real carbon structure. For nitrogen, the effect of carbon surface chemical composition is observed due to the quadrupole moment of this molecule, and this effect shifts the PSD curves compared to Ar. The largest differences are seen for CO2, and it is clearly demonstrated that the PSD curves obtained from adsorption isotherms of this molecule contain artificial peaks and the average pore diameter is strongly influenced by the presence of electrostatic adsorbate-adsorbate as well as adsorbate-adsorbent interactions.

Adsorption from aqueous solutions on opened carbon nanotubes: organic compounds speed up delivery of water from inside

We report the results of first systematic studies of organic adsorption from aqueous solutions onto relatively long single walled carbon nanotubes (four tubes, in initial and oxidised forms). Using molecular dynamics simulations (GROMACS package) we discuss the behaviour of tube-water as well as tube-adsorbate systems, for three different adsorbates (benzene, phenol and paracetamol).

Testing isotherm models and recovering empirical relationships for adsorption in microporous carbons using virtual carbon models and grand canonical Monte Carlo simulations

Using the plausible model of activated carbon proposed by Harris and co-workers and grand canonical Monte Carlo simulations, we study the applicability of standard methods for describing adsorption data on microporous carbons widely used in adsorption science. Two carbon structures are studied, one with a small distribution of micropores in the range up to 1 nm, and the other with micropores covering a wide range of porosity. For both structures, adsorption isotherms of noble gases (from Ne to Xe), carbon tetrachloride and benzene are simulated. The data obtained are considered in terms of Dubinin-Radushkevich plots. Moreover, for benzene and carbon tetrachloride the temperature invariance of the characteristic curve is also studied. We show that using simulated data some empirical relationships obtained from experiment can be successfully recovered. Next we test the applicability of Dubinin's related models including the Dubinin-Izotova, Dubinin-Radushkevich-Stoeckli, and Jaroniec-Choma equations. The results obtained demonstrate the limits and applications of the models studied in the field of carbon porosity characterization.

Hyper-parallel tempering Monte Carlo simulations of Ar adsorption in new models of microporous non-graphitizing activated carbon: effect of microporosity

The adsorption of gases on microporous carbons is still poorly understood, partly because the structure of these carbons is not well known. Here, a model of microporous carbons based on fullerene- like fragments is used as the basis for a theoretical study of Ar adsorption on carbon. First, a simulation box was constructed, containing a plausible arrangement of carbon fragments. Next, using a new Monte Carlo simulation algorithm, two types of carbon fragments were gradually placed into the initial structure to increase its microporosity. Thirty six different microporous carbon structures were generated in this way. Using the method proposed recently by Bhattacharya and Gubbins ( BG), the micropore size distributions of the obtained carbon models and the average micropore diameters were calculated. For ten chosen structures, Ar adsorption isotherms ( 87 K) were simulated via the hyper- parallel tempering Monte Carlo simulation method. The isotherms obtained in this way were described by widely applied methods of microporous carbon characterisation, i. e. Nguyen and Do, Horvath - Kawazoe, high- resolution alpha(a)s plots, adsorption potential distributions and the Dubinin - Astakhov ( DA) equation. From simulated isotherms described by the DA equation, the average micropore diameters were calculated using empirical relationships proposed by different authors and they were compared with those from the BG method.

The study of chiral adsorption systems using synchrotron- based structural and spectroscopic techniques: stereospecific adsorption of serine on Au-modified chiral Cu{531} surfaces

We apply modern synchrotron-based structural techniques to the study of serine adsorbed on the pure andAumodified intrinsically chiral Cu{531} surface. XPS and NEXAFS data in combination with DFT show that on the pure surface both enantiomers adsorb in l4 geometries (with de-protonated b-OH groups) at low coverage and in l3 geometries at saturation coverage. Significantly larger enantiomeric differences are seen for the l4 geometries, which involve substrate bonds of three side groups of the chiral center, i.e. a three-point interaction. The l3 adsorption geometry, where only the carboxylate and amino groups form substrate bonds, leads to smaller but still significant enantiomeric differences, both in geometry and the decomposition behavior. When Cu{531} is modified by the deposition of 1 and 2ML Au the orientations of serine at saturation coverage are significantly different from those on the clean surface. In all cases, however, a l3 bond coordination is found at saturation involving different numbers of Au atoms, which leads to relatively small enantiomeric differences.

The importance of attractive three-point interaction in enantioselective surface chemistry: stereospecific adsorption of serine on the intrinsically chiral Cu{531} surface

Both enantiomers of serine adsorb on the intrinsically chiral Cu{531} surface in two different adsorption geometries, depending on the coverage. At saturation, substrate bonds are formed through the two oxygen atoms of the carboxylate group and the amino group (μ3 coordination), whereas at lower coverage, an additional bond is formed through the deprotonated β−OH group (μ4 coordination). The latter adsorption geometry involves substrate bonds through three side groups of the chiral center, respectively, which leads to significantly larger enantiomeric differences in adsorption geometries and energies compared to the μ3 coordination, which involves only two side groups. This relatively simple model system demonstrates, in direct comparison, that attractive interactions of three side groups with the substrate are much more effective in inducing strong enantiomeric differences in heterogeneous chiral catalyst systems than hydrogen bonds or repulsive interactions.

Applicability of molecular simulations for modelling the adsorption of the greenhouse gas CF4 on carbons

Tetrafluoromethane, CF4, is powerful greenhouse gas, and the possibility of storing it in microporous carbon has been widely studied. In this paper we show, for the first time, that the results of molecular simulations can be very helpful in the study of CF4 adsorption. Moreover, experimental data fit to the results collected from simulations. We explain the meaning of the empirical parameters of the supercritical Dubinin–Astakhov model proposed by Ozawa and finally the meaning of the parameter k of the empirical relation proposed by Amankwah and Schwarz.

Complexes of NiX2 (X=Cl− and NO3−) with a NNO donor Schiff base: anion dependent structural variations and spectroscopic behaviour

Two new nickel(11) complexes, [NiLL'(H2O)(2)Cl] (1) and [{NiLL'(H2O)](2)(mu-H)]NO3·H2O(2), have been synthesized using a tridentate Schiff base ligand, HL, 2-[(2-dimethylamino-ethylimino)-methyl]-phenol, along with Cl- or NO3(-) as an anionic co-ligand or counter anion (where L'H = salicylaldehyde). Both complexes have been characterized by X-ray crystallography. The structural analyses reveal that complex 1 is mononuclear whereas 2 is a hydrogen-bridged dinuclear complex. The Ni(II) ions possess a distorted octahedral geometry in both structures. Both complexes show negative solvatochromic behaviour with increasing donor number (DN) of the solvent. In more coordinating solvents, like DMSO or methanol, the colour of the solutions is green, whereas in less coordinating solvents, like dichloromethane (DCM) or acetonitrile, it is red.

Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine ando-hydroxyacetophenone in NiII and CuII Complexes

Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]·2H2O (1) of mono-condensed tridentate Schiff baseligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the NiII as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)2·4H2O furnishing the complex [NiL(NCS)] (2) and with CuCl2·2H2O in the presence of NaN3 or NH4SCN producing [CuL(N3)]2 (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)2·6H2O and Cu(NO3)2·3H2O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)2·6H2O or Ni(NO3)2·6H2O to yield [Ni(hap)2] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, NiII possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around CuII in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around CuII is square pyramidal. In both 5 and 6, the CuII atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks.

Metalloporphyrin anion sensors: the effect of the metal centre on the anion binding properties of amide-functionalised and tetraphenyl metalloporphyrins

This article describes the synthesis and anion binding properties of a series of ‘picket fence’ metalloporphyrin complexes, within which the metal centre is systematically varied. The porphyrin structure contains four amide bonds and is the same for each metal. The anion binding properties of these receptors are further contrasted with those of their tetraphenylporphyrin congeners to elucidate both the effect of the metal centre and the influence of the amide groups on the anion recognition process. Anion binding was demonstrated using UV/visible and 1H NMR spectroscopies, electrochemistry and luminescence. The metal centre was found to be highly influential in the strength and selectivity of binding; for example, the cadmium and mercury complexes exhibited far greater affinities for anions than the zinc complexes in competitive solvents such as DMSO. The amide functionalities were found to enhance the anion binding process.