How N-(pyridin-4-yl)pyridin-4-amine and its methyl and nitro derivatives are arranged in the interlayer space of zirconium sulfophenylphosphonate: a problem solved by experimental and calculation methods.

Classical molecular simulation methods were used for a description of an arrangement of intercalated molecules N-(pyridin-4-yl)pyridin-4-amine (AH) and its derivatives, 3-methyl-N-(pyridin-4-yl)pyridin-4-amine (AMe), and 3-nitro-N-(pyridin-4-yl)pyridin-4-amine (ANO2) within a layered structure of zirconium 4-sulfophenylphosphonate. The intercalated molecules were placed between SO3H groups of the host layers. Their mutual positions and orientations were solved by molecular simulation methods and compared with the presented experimental results. Final calculated data showed differences of partially disordered arrangement of the intercalated molecules between zirconium 4-sulfophenylphosphonate layers. The calculation results revealed a dense net of hydrogen bonds connecting water molecules and the guests in the interlayer space and the sulfo groups of the host layers. We calculated the dipole moments of the AH, AMe and ANO2 guests in the final models in order to illustrate potential use of these materials in non-linear optics.

Exfoliation of layered mixed zirconium 4-sulfophenylphosphonate phenylphosphonates.

Mixed zirconium 4-sulfophenylphosphonate phenylphosphonates with formulae Zr(HO3SC6H4PO3)1.8(C6H5PO3)0.2·2.6H2O, Zr(HO3SC6H4PO3)1.3(C6H5PO3)0.7·2H2O, and Zr(HO3SC6H4PO3)0.7(C6H5PO3)1.3·3.6H2O (generally, ZrSPhP) were intercalated with a series of amino alcohols, H2N(CH2)nOH, where n = 2 to 6, and triethylamine. It was found that in the case of amino alcohols the basal spacing of the intercalates increases linearly with n. The intercalates prepared can be exfoliated either by sonication or by the action of high-shear forces. The use of a high-shear force disperser is a more efficient exfoliation method, as it provides lamellas with larger lateral dimensions in a much shorter time. It was found that amino alcohols provide roughly the same results regardless of the length of their carbon chain. As follows from atomic force microscopy measurements, triethylamine is the most appropriate exfoliation agent for ZrSPhP as it produces platelets with the largest lateral size and the lowest amount of defects.

Layered calcium phenylphosphonate: a hybrid material for a new generation of nanofillers.

The use of nanosheets of layered calcium phenylphosphonate as a filler in a polymeric matrix was investigated. Layered calcium phenylphosphonate (CaPhP), with chemical formula CaC6H5PO3∙2H2O, is a hybrid organic-inorganic material that exhibits a hydrophobic character due to the presence of phenyl groups on the surface of the layers. In this paper, various CaPhP synthesis methods were studied with the aim of obtaining a product most suitable for its subsequent exfoliation. The liquid-based approach was used for the exfoliation. It was found that the most promising technique for the exfoliation of CaPhP in an amount sufficient for incorporation into polymers involved using propan-2-ol with a strong shear force generated in a high-shear disperser. The filler was tested both in its unexfoliated and exfoliated forms for the preparation of polymer composites, for which a low molecular weight epoxy resin based on bisphenol A was used as a polymer matrix. The prepared samples were characterized by powder X-ray diffraction, atomic force microscopy, optical and scanning electron microscopy, and dynamic mechanical analysis. Flammability and gas permeation tests were also performed. The addition of the nanofiller was found to influence the composite properties - the exfoliated particles were found to have a higher impact on the properties of the prepared composites than the unexfoliated particles of the same loading.

Outerly functionalized and non-functionalized boron clusters intercalated into layered hydroxides with different modes of binding: materials for superacid storage.

Two binary boron hydrides (NH4)2B10H10 and Na2B12H12 and mono- and dicarboxy p- and m-carboranes (namely, 1-(COOH)-closo-1,7-C2B10H11, 1,12-(COOH)2-closo-1,12-C2B10H10 and 1,7-(COOH)2-closo-1,7-C2B10H10) were intercalated into ZnAl-layered double hydroxides (ZnAl-LDH) and into Zn5(OH)8(NO3)2·2H2O. The formed compounds were characterized using elemental analysis, thermogravimetry analysis, X-ray powder diffraction, infrared spectroscopy and solid state NMR. All the intercalated boron compounds are present in the interlayer space of the layered hosts as anions. It is presumed that in the case of B10H102-, B12H122- and 1,12-(COO)2-closo-1,12-C2B10H102-, the guest molecules form a monolayer, whereas in the case of 1-(COO)-closo-1,7-C2B10H111- and 1,7-(COO)2-closo-1,7-C2B10H102- a bilayer arrangement is more probable. In the case of 1,7-(COO)2-closo-1,7-C2B10H102-, the guest molecules are strongly interdigitated resulting in lowering of the interlayer distance. Two different modes of binding were found. Whereas the carboxylate derivatives of p- and m-carboranes are bonded through classical hydrogen bonds, the corresponding parent borane anions interact with the host structures by mainly dihydrogen bonding. In effect, both kinds of hydrogen bonding are mainly of an electrostatic nature. The dihydrogen bond is detected, e.g. in crystal engineering, and represents a driving force for interactions of boranes with biomolecules. Since the latter dicarboxylic acids were found to be superacids, their interactions with the host structures should be stronger than in the case of the benzoic and terephthalic acid intercalates.

Alkaline-earth metal phenylphosphonates and their intercalation chemistry.

The intercalation chemistry of layered alkaline-earth metal phenylphosphonates with the general formula MeC6H5PO3·2H2O (Ca, Sr, Ba) is reviewed. The preparation of the host materials is described and their behavior in dependence on the relative humidity and pH of the reaction medium is discussed. Mutual relationships between MeC6H5PO3·2H2O and Me(C6H5PO3H)2 were investigated using a method of computer-controlled addition of reagents. The MeC6H5PO3·2H2O compounds are able to intercalate species having a free electron pair through the so-called coordination intercalation. In this way, 1-alkylamines, 1-alkanols, 1,n-diols and 1,2-diols were intercalated. In the case of the ethanol and methanol intercalates of strontium phenylphosphonate we were able to determine the structure of the host part by single-crystal X-ray diffraction. By combination of the data obtained from the diffraction with molecular modeling we suggested the arrangement of the host molecules in the interlayer space of the host. The arrangement of the shorter diols in the interlayer space of strontium phenylphosphonate was also proposed on the basis of molecular modeling calculations. These models help us to understand the structure of the prepared intercalates.

Geometry optimization of zirconium sulfophenylphosphonate layers by molecular simulation methods.

Classical molecular simulation methods were used for a detailed structural description of zirconium 4-sulfophenylphosphonate and zirconium phenylphosphonate 4-sulfophenylphosphonates with general formula Zr(HO3SC6H4PO3) x (C6H5PO3)2-x ·yH2O (x = 0.7-2; y = 0 or 2). First, models describing the structure of zirconium 4-sulfophenylphosphonate (x = 2) were calculated for the hydrated (y = 2) and dehydrated (y = 0) compounds. Subsequently, models for two mixed zirconium phenylphosphonate 4-sulfophenylphosphonates (x = 1.3 and 0.7) were calculated. Optimized models suggest that the presence of water molecules between sulfo groups creates a water-sulfonate layer with a system of hydrogen bonds. We suppose that this arrangement is the reason for a higher proton conductivity of the hydrated samples compared to dehydrated samples. When the water molecules are removed, a small decrease in the basal spacing (around 0.06 Å) is observed. This behavior is confirmed by the simulated models, where no significant changes in the structure on dehydration were observed except the absence of the water molecules and a lower number of hydrogen bonds between two adjacent sulfonate sheets. Due to the good crystallinity of the samples and the presence of sharp non-basal peaks in their X-ray diffraction patterns, Miller indices of the non-basal peaks in the diffraction patterns calculated from the models can be compared with those found in the experimental data. This allowed us to precisely describe for example (15 5-2) planes, from which mutual distances of the phenyl rings were determined to be 2.62 Å. Graphical Abstract Detailed ball and stick view into the interlayer structure of ZrSPhP1.3.

Synthesis and characterization of new barium methylphosphonates.

Eight new barium methylphosphonates were prepared and described. In dependence on pH, either barium hydrogen methylphosphonates or barium methylphosphonates can be formed. In the case of barium methylphosphonates, BaCH3PO3·3H2O crystallizes from the solution at room temperature and BaCH3PO3·H2O at a temperature above 65 °C. On heating, these hydrates form two anhydrous barium methylphosphonates (α-BaCH3PO3 and ß-BaCH3PO3) with the same composition but with a different structure. In a basic environment, barium hydrogen methylphosphonate monohydrate, Ba(CH3PO3H)2·H2O, transforms to BaCH3PO3·3H2O through an intermediate with the formula Ba2(CH3PO3H)2(CH3PO3)·4H2O. The reverse reaction, that is the reaction of BaCH3PO3·3H2O with methylphosphonic acid, proceeds to the intermediate only and hydrogen methylphosphonate is not formed. Acidic Ba(CH3PO3H)2·H2O is able to interact with basic amines and form stable intercalates with them. Structures of ß-BaCH3PO3 (P21/c, a = 8.4501(6) Å, b = 7.2555(7) Å, c = 7.4604(8) Å, ß = 99.837(8)°, Z = 4) and BaCH3PO3·H2O (P21/c, a = 20.5077(5) Å, b = 7.2175(2) Å, c = 7.4909(3) Å, ß = 95.522(3)°, Z = 8) were solved from powder X-ray diffraction data. Both compounds are layered, and the layers are formed of two sheets of Ba atoms connected through oxygen atoms of the phosphonate groups. The methyl groups point towards the interlayer space. In the case of BaCH3PO3·H2O, the molecules of water are coordinated to the Ba atoms and are placed in the interlayer space among the methyl groups.

Influence of 1,2-alkanediols on the structure of their intercalates with strontium phenylphosphonate solved by molecular simulation and experimental methods.

Strontium phenylphosphonate intercalates with 1,2-diols (from 1,2-ethanediol to 1,2-hexanediol) were synthesized and characterized by X-ray diffraction, thermogravimetry, chemical analysis, and molecular simulation methods. Prepared samples exhibit a very good stability at ambient conditions. Structural arrangement calculated by simulation methods suggested formation of cavities surrounded by six benzene rings. Each cavity contained one molecule of diol and one molecule of water for the 1,2-ethanediol to 1,2-butanediol intercalates. In the case of 1,2-pentanediol two types of cavities alternated: one with diol molecules and another one with two water molecules. In the 1,2-hexanediol intercalate the benzene rings created two types of cavities containing one or two diol molecules, respectively, and this conformational variability led to a more disordered arrangement with respect to the models with shorter alkyl chains. Coordination of the oxygen atoms of the diols to the strontium atoms of the host follows the same pattern for all 1,2-diol intercalates except the 1,2-hexanediol intercalate, where these oxygen atoms can be mutually exchanged at their positions. The calculated basal spacings and structural models are in good agreement with experimental basal spacings obtained from X-ray powder diffraction and with other experimental results.

Intercalation of 1,n-diols into strontium phenylphosphonate: how the shape of the host layers influences arrangement of the guest molecules.

Strontium phenylphosphonate intercalates with 1,n diols (n=2-4, 6-8) having general formula SrC6H5PO3⋅x(HO(CH2)nOH)⋅yH2O were prepared by precipitation from strontium phenylphosphonate solution and the corresponding diols. Prepared compounds exhibit a very good stability at ambient conditions. The intercalates were characterized by X-ray diffraction, thermogravimetry and elemental analysis. Thanks to the existence of free spaces among the benzene rings the diols exhibit a peculiar intercalation behavior. This behavior is explained on the basis of molecular simulation, which facilitated to elucidate the arrangement of the diol (guest) molecules in the specifically shaped space between the layers of the host material. From the structural point of view the intercalates can be divided into two subgroups: (i) intercalates with 1,2- to 1,4-diols and (ii) intercalates with 1,6- to 1,8-diols. The alkanediols of the first group are immersed in the free spaces among the benzene groups, their molecules adopt a horseshoe shape meaning cis conformation and are bonded by both of their OH groups to one host layer. The longer alkanediol chains of the second group allow anchoring to both neighboring layers of the host forming a kind of pillared structure in the interlayer space. The diol molecules are in this case bonded to the host layers by their OH groups to the oxygen atoms of the host layers and to water molecules present in the interlayer space through hydrogen bonds. The values of the basal spacing obtained from the experimental powder X-ray patterns are in a very good agreement with the basal spacing values calculated from the models. The molecular simulation of a 1,5-pentanediol intercalate, which we were not be able to synthesize, explained why this intercalate cannot be stable.

Organization and intramolecular charge-transfer enhancement in tripodal tris[(pyridine-4-yl)phenyl]amine push-pull molecules by intercalation into layered materials bearing acidic functionalities.

Two new intercalates of tris[4-(pyridin-4-yl)phenyl]amine (TPPA) with zirconium hydrogen phosphate and zirconium 4-sulfophenylphosphonate having formulae Zr(HPO4)2·0.21(C33H24N4)·2.5H2O and Zr(HO3SC6H4PO3)(1.3)(C6H5PO3)(0.7)·0.35(C33H24N4)·2.5H2O were prepared and characterized by thermogravimetry, IR spectroscopy, and powder X-ray diffraction. The TPPA molecule has been selected as a model tripodal push-pull system with three peripheral basic centers that may undergo protonation. Their protonation/quaternization afforded HTPPA/MeTPPA molecules with enhanced intramolecular charge-transfer (ICT), which has been documented by electrochemical measurements, UV-Vis spectra and calculated properties such as the HOMO/LUMO levels and the first and second hyperpolarizabilities. Intercalation of TPPA into layered zirconium hydrogen phosphate and zirconium 4-sulfophenylphosphonate led to its significant organization and protonation as shown by the IR spectra. From the powder X-ray data we can deduce that the TPPA molecules are placed in the interlayer space of both hosts by anchoring two peripheral nitrogen atoms to one host layer and the opposite pyridine-4-yl terminus to the other neighboring host layer. In zirconium 4-sulfophenylphosphonate, the TPPA molecules are oriented perpendicularly, while in zirconium phosphate these molecules are slanted with respect to the layers of the host. On dehydration by heating, the interlayer distance of the intercalate decreases, which indicates a further slanting of the TPPA molecules. It follows from the UV-Vis spectra that TPPA is present in both intercalates in an equilibrium of protonated and non-protonated forms. The described materials represent the first case when a tripodal push-pull system was incorporated into a system with restricted geometry with the aim to influence its optical properties.

Alkaline-earth metal phosphonocarboxylates: synthesis, structures, chirality, and luminescence properties.

Six new alkaline-earth metal carboxyphosphonates [Mg(H2O)(H2PMIDA)] (1), [Sr(H2O)(H2PMIDA)] (2), [Sr2(H2O)(PMIDA)] (3), [Sr2(HPO4)(H2PMIDA)] (4), [Ba2(HPO4)(H2PMIDA)] (5), and [Ba2(H2O)(H2PMIDA)2] (6) (H4PMIDA = N-(phosphonomethyl)iminodiacetic acid) have been synthesized solvothermally in order to study the coordination behavior of H4PMIDA towards alkaline-earth metal ions (Mg(2+), Sr(2+), and Ba(2+)) and the structural features of the resulting polymeric compounds. The newly synthesized compounds have been characterized by elemental analysis, UV-Vis spectrometry, IR spectroscopy, thermogravimetry analysis, solid state (31)P MAS NMR, powder X-ray diffraction analysis and single crystal X-ray diffraction techniques. The single crystal structure analysis revealed structural variability of the prepared compounds. Compounds 1, 2, 4 and 5 are three-dimensional with the H2PMIDA skeletons connecting the inorganic parts to each other, whereas compound has a layered structure. Compounds 2, 4 and 5 contain helical structural motifs. In addition, the extrinsic luminescent properties of Eu(III)- and Tb(III)-doped compounds 1, 4 and 5 have also been studied.

Untypical [VOPO4]- layer in vanadyl phosphates with variant interlayer gap of double-tiered template.

Four new organically templated layered vanadyl(IV) phosphates, (Hcha)VOPO(4) x 0.5 H(2)O (cha = cyclohexylamine) (1), (Hchpa)VOPO(4) x 0.5 H(2)O (chpa = cycloheptylamine) (2), (Hcha)(0.5)(Hchpa)(0.5)VOPO(4) x 0.5 H(2)O (3), and (H(2)aepip)[(VOPO(4))(2)(H(2)O)] x H(2)O (aepip = N-(2-aminoethyl)piperazine) (4), have been synthesized under mild hydrothermal conditions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, magnetic susceptibility, and electron paramagnetic resonance (EPR) spectroscopy. They displayed a large interlayer gap propped up by an unprecedented double-tiered monoamine in vertical angles generating the lightest layered VPO material ever prepared and characterized. The anionic [VOPO(4)](-) sheets for all four compounds are constructed by a common secondary building unit consisting of one copper-acetate-type {(V(IV)O)(2)(mu(2)-PO(4))(4)} cluster and two vanadium polyhedra. The d(1) state was confirmed by both magnetic susceptibility studies and EPR spectra. Moreover, compounds 1 and 4 showed antiferromagnetism with T(N) at 30 K, the highest ever observed in layered vanadyl phosphates. The structural relationship, template arrangement, magnetic property, thermal stability, and correlation between interlayer gaps and densities are discussed. Compounds 1-3 crystallized in the monoclinic space group P2(1)/c (no. 14) with Z = 8, whereas compound 4 crystallized in the orthorhombic space group Pbca (no. 61) with Z = 4. Crystal data of 1, a = 16.3461(9) A, b = 14.2641(8) A, c = 9.4037(5) A, beta = 94.519(1) degrees, V = 2185.8(2) A(3); 2, a = 17.0773(5) A, b = 14.3449(4) A, c = 9.4251(3) A, beta = 93.976(1) degrees, V = 2303.3(1) A(3); 3, a = 16.6765(4) A, b = 14.2927(3) A, c = 9.4120(3) A, beta = 95.389(1) degrees, V = 2233.5(1) A(3); 4, a = 14.2517(9) A, b = 9.4012(6) A, c = 24.442(2) A, V = 3274.8(4) A(3).

Structure analysis of hydrotalcite intercalated with pyrenetetrasulfonate; experiments and molecular modelling.

The structure of pyrenetetrasulfonate intercalated with hydrotalcite, having the formula [Zn(0.68)Al(0.32)(OH)(2)][(C(16)H(6)O(12)S(4))(0.08) . x H(2)O], was proposed based on molecular simulations combined with experimental data (X-ray powder diffraction, thermogravimetry). Calculations were done for samples kept at various relative humidities (0%, 84%, 98%). The appropriate models were selected from comparison of calculated and measured diffraction patterns. Modelling revealed the arrangement of pyrenetetrasulfonate anions, and the positions and the amount of water molecules in the interlayer space of the host structure. The results confirmed a large variability in the arrangement of the guest species. In the sample without water molecules (0% RH), pyrenetetrasulfonate anions formed a layer at the centre of the interlayer distance. For the sample kept at 84% RH, the anions formed two layers at the thirds of the interlayer. For the sample kept at 98% RH, the anions became tilted with respect to the layered double hydroxides (LDH) layers and are less organised. Water molecules were arranged in three distinct planes: one in the middle and two at the quarters of interlayer distance. The number of water molecules obtained by the modelling basically agrees with the water content as measured by thermogravimetry.

Layered double hydroxide intercalated with p-methylbenzoate and p-bromobenzoate: molecular simulations and XRD analysis.

Samples of Mg4Al2 layered double hydroxide (LDH) intercalated with p-methylbenzoate and p-bromobenzoate anions were prepared by reconstruction of calcined LDH. The interlayer arrangement of guests was investigated by molecular modeling combined with X-ray powder diffraction and thermogravimetry. Molecular modeling was carried out in a Cerius2 modeling environment. In both structures the guest anions adopt a nearly perpendicular arrangement of their long axis with respect to the host layers and they are anchored to the OH groups of the layers through COO* groups via electrostatic interactions. Molecular modeling revealed that both structures of the intercalates exhibit a certain disorder of guest anions in the interlayer space. In the case of LDH-p-methylbenzoate intercalate the anions tend to be situated in disordered rows, and the LDH-p-bromobenzoate intercalate exhibits a total disorientation of guest anions. A good agreement between calculated and measured X-ray diffraction patterns and between experimental and calculated basal spacings was obtained. In the LDH-p-methylbenzoate intercalate d exp=16.96 A and d calc=16.97 A, and in the case of LDH-p-bromobenzoate intercalate d exp=17.19 A and d calc=17.40 A.

Synthesis and characterization of new calcium phenylphosphonates and 4-carboxyphenylphosphonates.

Three new calcium phenylphosphonates, CaC(6)H(5)PO(3).2H(2)O, Ca(3)(C(6)H(5)PO(3)H)(2)(C(6)H(5)PO(3))(2).4H(2)O, and CaC(6)H(5)PO(3).H(2)O, and two calcium 4-carboxyphenylphosphonates, Ca(HOOCC(6)H(4)PO(3)H)(2) and Ca(3)(OOCC(6)H(4)PO(3))(2).6H(2)O, were prepared. It was found that CaC(6)H(5)PO(3).2H(2)O transformed into previously known Ca(C(6)H(5)PO(3)H)(2) via Ca(3)(C(6)H(5)PO(3)H)(2)(C(6)H(5)PO(3))(2).4H(2)O in the presence of phenylphosphonic acid, and vice versa, Ca(C(6)H(5)PO(3)H)(2) turned into CaC(6)H(5)PO(3).2H(2)O in a weak basic medium. A similar relationship was found between Ca(HOOCC(6)H(4)PO(3)H)(2) and Ca(3)(OOCC(6)H(4)PO(3))(2).6H(2)O; i.e., Ca(3)(OOCC(6)H(4)PO(3))(2).6H(2)O transformed into Ca(HOOCC(6)H(4)PO(3)H)(2) in the presence of 4-carboxyphenylphosphonic acid. On the contrary, Ca(3)(OOCC(6)H(4)PO(3))(2).6H(2)O is formed from Ca(HOOCC(6)H(4)PO(3)H)(2) in the presence of ammonium as a weak base. The structure of Ca(HOOCC(6)H(4)PO(3)H)(2) was solved from X-ray powder diffraction data by an ab initio method using a FOX program. The compound is monoclinic, space group C2/c (No. 15), a = 49.218(3) A, b = 7.7609(4) A, c = 5.4452(3) A, beta = 128.119(3) degrees , and Z = 4. Its structure is one-dimensional with [Ca(2)(HOOCC(6)H(4)PO(3)H)(4)](infinity) ribbons forming basic building blocks. The ribbons are held together by hydrogen bonds between carboxylic groups.

Intercalation of cyclic ethers into vanadyl phosphate.

Two cyclic ethers, tetrahydrofuran (THF) and tetrahydropyran (THP), were intercalated into vanadyl phosphate and characterized by X-ray powder diffraction, thermogravimetry, and IR and Raman spectroscopy. Both compounds contain one molecule of ether per formula unit of VOPO(4) and show high thermal stability in comparison with VOPO(4) intercalates with other organic guest molecules. Both ethers are anchored to the VOPO(4) host layers by their oxygen atoms, which are coordinated to the vanadium atoms of the host. The probable arrangement of the tetrahydropyran molecules in the host interlayer space is derived from molecular simulations by the Cerius(2) 4.5 program.

Preparation and Probable Structure of Layered Complexes of Vanadyl Phosphate with 1-Alkanols and 1,omega-Alkanediols.

The direct reaction of liquid (or melted solid) 1-alkanols or 1,omega-alkanediols with solid finely ground VOPO(4). 2H(2)O in a microwave field leads to layered complexes of the composition VOPO(4).2C(n)()H(2)(n)()(+1)OH (n = 1-18) or VOPO(4).C(n)()H(2)(n)()(OH)(2) (n = 2-10), respectively. The results of X-ray diffraction analysis show that the structures of all of these polycrystalline complexes (intercalates) retain the original layers of (VOPO(4))(infinity). The molecules of alcohols are placed between the host layers in a bimolecular way, being anchored to them by donor-acceptor bonds between the oxygen atom of an OH group and a vanadium atom as well as by hydrogen bonds. The molecules of diols, on the other hand, using similar bonds, form, in monomolecular arrangement, bridges linking the adjacent layers of the host. The aliphatic chains of both intercalated alcohol and diol molecules possess all-trans configurations, and their axes are perpendicular to the host layers.