Hydrogen bonds and local symmetry in the crystal structure of gibbsite

First‐principles quantum mechanical calculations of NMR chemical shifts and quadrupolar parameters have been carried out to assign the ²⁷Al MAS NMR resonances in gibbsite. The ²⁷Al NMR spectrum shows two signals for octahedral aluminum revealing two aluminum sites coordinated by six hydroxyl groups each, although the crystallographic positions of the two Al sites show little difference. The presence of two distinguished ²⁷Al NMR resonances characterized by rather similar chemical shifts but quadrupolar coupling constants differing by roughly a factor of two is explained by different character of the hydrogen bonds, in which the hydroxyls forming the corresponding octahedron around each aluminum site, are involved. The Al‐I site characterized by a C_Q = 4.6 MHz is surrounded by OH? groups participating in four intralayer and two interlayer hydrogen bonds, while the Al‐II site with the smaller quadrupolar constant (2.2 MHz) is coordinated by hydroxides, of which two point toward the intralayer cavities and four OH‐bonds are aligned toward the interlayer gallery. In high‐resolution solid‐state ¹H CRAMPS (combination of rotation and multiple‐pulse spectroscopy) four signals with an intensity ratio of 1:2:2:1 are resolved which allow to distinguish six nonequivalent hydrogen sites reported in the gibbsite crystal structure and to ascribe them to two types of structural OH groups associated with intralayer and interlayer hydrogen bonds. This study can be applied to characterize the gibbsite‐like layer—intergallery interactions associated with hydrogen bonding in the more complex systems, such as synthetic aluminum layered double hydroxides. Copyright © 2010 John Wiley & Sons, Ltd.     

Analysis of the spin exchange interactions and the ordered magnetic structures of lithium transition metal phosphates LiMPO4 (M = Mn, Fe, Co, Ni) with the olivine structure

The olivine-type compounds LiMPO4 (M = Mn, Fe, Co, Ni) consist of MO4 layers made up of corner-sharing MO6 octahedra of high-spin M2+ ions. To gain insight into the magnetic properties of these phosphates, their spin exchange interactions were estimated by spin dimer analysis using tight binding calculations and by electronic band structure analysis using first principles density functional theory calculations. Three spin exchange interactions were found to be important for LiMPO4, namely, the intralayer superexchange J1, the intralayer super-superexchange Jb along the b-direction, and the interlayer super-superexchange J2 along the b-direction. The magnetic ground state of LiMPO4 was determined in terms of these spin exchange interactions by calculating the total spin exchange interaction energy under the classical spin approximation. In the spin lattice of LiMPO4, the two-dimensional antiferromagnetic planes defined by the spin exchange J1 are antiferromagnetically coupled by the spin exchange J2, in agreement with available experimental data.     

Substituent effects on the electronic characteristics of pentacene derivatives for organic electronic devices: dioxolane-substituted pentacene derivatives with triisopropylsilylethynyl functional groups

The intramolecular electronic structures and intermolecular electronic interactions of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene), 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]-pentacene (TP-5 pentacene), and 2,2,10,10-tetraethyl-6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5 pentacene) have been investigated by the combination of gas-phase and solid-phase photoelectron spectroscopy measurements. Further insight has been provided by electrochemical measurements in solution, and the principles that emerge are supported by electronic structure calculations. The measurements show that the energies of electron transfer such as the reorganization energies, ionization energies, charge-injection barriers, polarization energies, and HOMO-LUMO energy gaps are strongly dependent on the particular functionalization of the pentacene core. The ionization energy trends as a function of the substitution observed for molecules in the gas phase are not reproduced in measurements of the molecules in the condensed phase due to polarization effects in the solid. The electronic behavior of these materials is impacted less by the direct substituent electronic effects on the individual molecules than by the indirect consequences of substituent effects on the intermolecular interactions. The ionization energies as a function of film thickness give information on the relative electrical conductivity of the films, and all three molecules show different material behavior. The stronger intermolecular interactions in TP-5 pentacene films lead to better charge transfer properties versus those in TIPS pentacene films, and EtTP-5 pentacene films have very weak intermolecular interactions and the poorest charge transfer properties of these molecules.     

Metamagnetism in hydrophobically induced carboxylate (phenylmalonate)-bridged copper(II) layers

Self-assembly of copper(l) ions, phenylmalonate and pyrimidine yields the layered compound [Cu(pym)(Phmal)n (1) where intralayer ferro- and interlayer antiferromagnetic interactions occur with three-dimensional antiferromagnetic ordering at T(c) = 2.15 K.     

Effect of temperature on the conformation of dibenzotropone adsorbed on montmorillonites

The nature of the adsorption complex formed between dibenzotropone (DBT) and montmorillonite at elevated temperatures is strongly dependent on the interlayer cations. This was shown by electronic and IR spectra, by X-ray diffraction, and by study of the effects of gradual heating of the samples on these analyses. All samples exhibited significant red shifts of the electronic spectra of DBT into the visible range. These red shifts are attributed to two factors, both contributing to the enhancement of the tropylium planar character of DBT: hydrogen-bonding of acidic interlayer water to the carbonyl group, imparting positive charge to the tropone ring; and π interactions between the aromatic moiety and the oxygen planes. The position of the maximum was temperature-dependent for Cu-, Ni-, Al- and Fe-montmorillonites, for which heating (100°) under vacuum increased the red shift. The organic molecule assumes a planar conformation and is oriented parallel to the clay layers. IR spectra confirming this conformational orientation of DBT are discussed. The basal spacings of the DBT montmorillonite associations depend on the number of water and DBT sheets present in the interlayers. Layers with one or two sheets of DBT and with up to two sheets of water could be distinguished, leading to a maximum spacing of 20.4 Å.     

Variable interlayer distance of intercalates of naphthalenedisulfonate isomers in hydrotalcite-like Zn and Al layered double-hydroxides

Three isomers of naphthalenedisulfonates (naphthalene-2,6-,-1,5- and -2,7-disulfonates; abbreviated as N26DS, N15DS and N27DS, respectively, and collectively abbreviated as NijDS) are intercalated in the interlayer region of Zn and Al layered double-hydroxides (Zn/Al-LDH). The intercalated products are obtained under weak alkaline conditions as precipitates from reaction mixtures containing one of the isomers and calcined powder prepared by using carbonate-intercalated Zn/Al-LDH. When N26DS or N15DS is intercalated, two solid phases are observed which have different values of basal spacing in powder X-ray diffraction (XRD) patterns, whereas only one phase appears when N27DS is intercalated. The different basal spacing results from one of two alternate orientations taken by the interlayer NijDS. One of the two phases appears exclusively in XRD patterns, although the other is produced together with a by-product. A more closely packed orientation is suggested for the interlayer guest molecules in the latter phase. The solid state chemistry has been investigated using UV visible diffuse reflection (DR) spectroscopy, differential thermal analysis/thermogravimetry (DTA/TG) and X-ray photoelectron spectroscopy (XPS).     

Thermally induced solid-state phase transition of bis(triisopropylsilylethynyl) pentacene crystals

Bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) is a functionalized pentacene derivative designed to enhance both the solution solubility and solid-state packing of pentacene. In this paper, we report our observations of a solid-state phase transition in TIPS pentacene crystals upon heating or cooling. Evidence from differential scanning calorimetry (DSC), hot-stage optical microscopy, as well as high-temperature X-ray and electron diffraction are presented. A reasonable match with experimental data is obtained with molecular modeling. Our results reveal that the transition is associated with a conformational reorganization of the TIPS side groups, accompanied by a slight decrease in the acene-to-acene spacing and a shift of the overlap between the neighboring pentacene units. The observed cracking should be avoided or minimized in TIPS pentacene-based thin film transistors to maintain their relatively high charge carrier mobility.     

Importance of weak interactions in developing 1,3-bis(4,6-dimethyl-1H-nicotinonitrile-1-yl)1,3-dioxy propane polymorphs

The structure of 1,3-bis(4,6-dimethyl-1H-nicotinonitrile-1-yl)1,3-dioxy propane polymorphs has been characterized by X-ray diffraction, FT-IR, 1H and 13C NMR spectroscopies. The influence of intra and intermolecular weak interactions is thoroughly studied in solid state using single crystal X-ray diffraction and FT-IR. These polymorphs belong to monoclinic space group 'P2(1/n)' and 'P2(1/c)'. These polymorphs have C-H?n (lone pair), hydrogen bonds, C-N?π, C-H?π and π?π intermolecular non-covalent interactions. These polymorphs are the result of weak interactions and solvent used in crystallization. The FT-IR spectra have been recorded in the solid phase and NMR has been recorded in solvent. The optimized geometry has been calculated by B3LYP methods using different basis sets. The FT-IR and NMR spectra of 1st polymorphs has been calculated at B3LYP/6-31G (d) level. The scaled theoretical wave number showed good agreement with the experimental values. These two polymorphs as well as other stereomers are studied by DFT calculations.     

Collective and individual plasmon resonances in nanoparticle films obtained by spin-assisted layer-by-layer assembly

Nanoscale uniform films containing gold nanoparticle and polyelectrolyte multilayer structures were fabricated by the using spin-assembly or spin-assisted layer-by-layer (SA-LbL) deposition technique. These SA-LbL films with a general formula [Au/(PAH-PSS)nPAH]m possessed a well-organized microstructure with uniform surface morphology and high surface quality at a large scale (tens of micrometers across). Plasmon resonance peaks from isolated nanoparticles and interparticle interactions were revealed in the UV-visible extinction spectra of the SA-LbL films. All films showed the strong extinction peak in the region of 510-550 nm, which is due to the plasmon resonance of the individual gold nanoparticles redshifted because of a local dielectric environment. For films with sufficient density of gold nanoparticles within the layers, the second strong peak was consistently observed between 620 and 660 nm, which is the collective plasmon resonance from intralayer interparticle coupling. Finally, we suggested that, for certain film designs, interlayer interparticle resonance might be revealed as an independent contribution at 800 nm in UV-visible spectra. The observation of independent and concurrent individual, intralayer, and interlayer plasmon resonances can be critical for sensing applications, which involve monitoring of optomechanical properties of ultrathin optically active compliant membranes.     

Chiral molecular magnets: synthesis, structure, and magnetic behavior of the series [M(L-tart)] (M = Mn(II), Fe(II), Co(II), Ni(II); L-tart = (2R,3R)-(+)-tartrate)

A new series of layered magnets with the formula [M(L-tartrate)] (M = Mn(II), Co(II), Fe(II), Ni(II); L-tartrate = (2R,3R)-(+)-tartrate) has been prepared. All of these compounds are isostructural and crystallize in the chiral orthorhombic space group I222, as found by X-ray structure analysis. Their structure consists of a three-dimensional polymeric network in which each metal shows distorted octahedral coordination bound to four L-tartrate ligands, two of which chelate through an alcohol and a carboxylate group and the other two bind terminally through a monodentate carboxylate group. The chirality of the ligand imposes a Delta conformation on all metal centers. Magnetically, the paramagnetic metal centers form pseudotetragonal layers in which each metal is surrounded by four other metals, with syn,anti carboxylate bridges. These salts show intralayer antiferromagnetic or ferromagnetic interactions, depending on the electronic configuration of the metal, and weak interlayer antiferromagnetic interaction. In all cases the magnetic properties are strongly affected by the anisotropy of the system, and the presence of magnetic canting has been found. The Mn derivative behaves as a weak ferromagnet with a critical temperature of 3.3 K. The Ni derivative shows very unusual magnetic behavior in that it exhibits antiferromagnetic ordering below 6 K, the onset of spontaneous magnetization arising from spin reorientation into a canted phase below 4.5 K, and a field-induced ferromagnetic state above 0.3 T at 2 K, behavior typical of metamagnets. The Fe and Co derivatives show antiferromagnetic interactions between spin carriers, but do not order above 2 K.     

Synchrotron X-ray Electron Density Analysis of Chemical Bonding in the Graphitic Carbon Nitride Precursor Melamine

Melamine is a precursor and building block for graphitic carbon nitride (g-CN) materials, a group of layered materials showing great promise for catalytic applications. The synthetic pathway to g-CN includes a polycondensation reaction of melamine by evaporation of ammonia. Melamine molecules in the crystal organize into wave-like planes with an interlayer distance of 3.3 Å similar to that of g-CN. Here we present an extensive investigation of the experimental electron density of melamine obtained from modelling of synchrotron radiation X-ray single-crystal diffraction data measured at 25 K with special focus on the molecular geometry and intermolecular interactions. Both intra- and interlayer structures are dominated by hydrogen bonding and π-interactions. Theoretical gas-phase optimizations of the experimental molecular geometry show that bond lengths and angles for atoms in the same chemical environment (C−N bonds in the ring, amine groups) differ significantly more for the experimental geometry than for the gas-phase-optimized geometries, indicating that intermolecular interactions in the crystal affects the molecular geometry. In the experimental crystal geometry, one amine group has significantly more sp³-like character than the others, hinting at a possible formation mechanism of g-CN. Topological analysis and energy frameworks show that the nitrogen atom in this amine group participates in weak intralayer hydrogen bonding. We hypothesize that melamine condenses to g-CN within the layers and that the unique amine group plays a key role in the condensation process.     

Study of the structural and atomic diffusive properties of the ordered Cu3Au (110) surface

The structural properties, the formation and migration energies of a single vacancy migrating intralayer and interlayer in the CuAu‐terminated (110) surface of Cu₃Au ordered alloy have been calculated and discussed by using the modified analytical embedded‐atom method (MAEAM) and molecular dynamics (MD) methods. The surface layer exhibits rippling that the Au atoms are raised above Cu atoms about 0.117 Å in the topmost layer. The displacements of the topmost two layers are comparatively larger, while the third layer relaxes slightly and there are no changes in the nether layers. From energy minimization, the vacancy is most likely to be formed in the first layer (1L), especially on the Au site. The surface vacancy shows the smallest formation energy compared to the interlayer and bulk vacancies, while the corresponding value converges after the fifth layer (5L). For Cu vacancy originally sited in the second layer (2L) and migrated intralayer and interlayer, the diffusion without causing the local disorder is the most favorable, and the vacancy tends to migrate to the topmost layer. In the topmost layer of the CuAu‐terminated (110) surface, the circularity path is preferred over the beeline path. Copyright © 2011 John Wiley & Sons, Ltd.     

Revealing the Preferred Interlayer Orientations and Stackings of Two‐Dimensional Bilayer Gallium Selenide Crystals

Characterizing and controlling the interlayer orientations and stacking orders of two‐dimensional (2D) bilayer crystals and van der Waals (vdW) heterostructures is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) crystals that result from different layer stackings provide an ideal platform to study the stacking configurations in 2D bilayer crystals. Through a controllable vapor‐phase deposition method, bilayer GaSe crystals were selectively grown and their two preferred 0° or 60° interlayer rotations were investigated. The commensurate stacking configurations (AA′ and AB stacking) in as‐grown bilayer GaSe crystals are clearly observed at the atomic scale, and the Ga‐terminated edge structure was identified using scanning transmission electron microscopy. Theoretical analysis reveals that the energies of the interlayer coupling are responsible for the preferred orientations among the bilayer GaSe crystals.     

Topological analysis of chemical bonding in the layered FePSe3 upon pressure-induced phase transitions

Two pressure-induced phase transitions have been theoretically studied in the layered iron phosphorus triselenide (FePSe₃ ). Topological analysis of chemical bonding in FePSe₃ has been performed based on the results of first-principles calculations within the periodic linear combination of atomic orbitals (LCAO) method with hybrid Hartree-Fock-DFT B3LYP functional. The first transition at about 6 GPa is accompanied by the symmetry change from to C2/m , whereas the semiconductor-to-metal transition (SMT) occurs at about 13 GPa leading to the symmetry change from C2/m to . We found that the collapse of the band gap at about 13 GPa occurs due to changes in the electronic structure of FePSe₃ induced by relative displacements of phosphorus or selenium atoms along the c-axis direction under pressure. The results of the topological analysis of the electron density and its Laplacian demonstrate that the pressure changes not only the interatomic distances but also the bond nature between the intralayer and interlayer phosphorus atoms. The interlayer P–P interactions are absent in two non-metallic FePSe₃ phases while after SMT the intralayer P–P interactions weaken and the interlayer P–P interactions appear.     

有机分子膜层间相互作用对聚集体的影响

有机材料在分子设计与合成方面具有高度可塑性、灵活性及多样性,易于制成各种功能器件．带有电子给体和受体以及、电子体系的两亲类有机分子具有极高的超分子极化率“‘．利用Langmuir－Blodgett（LB）技术可实现有机材料在纳米尺寸上的分子组装,形成高度有序、非中心对称的LB膜以实现大的宏观二阶非线性极化系数．有机分子在LB膜中常常形成聚集体,而聚集体的存在将显著改变膜的宏观光学特性．根据有机分子间相互作用能的类型,聚集体可以分为J一型和H一型两种,分别表现为它们的吸收或荧光光谱‘”相对于单体发生红移或蓝移．近年来…     

Magnetic ordering in three-dimensional metal-organic frameworks based on carboxylate bridged square-grid layers

Three isomorphous metal-organic frameworks of formula [M(ppdc)(H(2)O)(2)](n) [M = Mn(II), Fe(II), and Co(II)] were synthesized from sodium p-phenylenediacrylic (Na(2)ppdc). Crystallographic studies revealed that the compounds are layer-pillared 3D frameworks in which the square-grid M(II) layers with single carboxylate bridges are interlinked by long organic spacers with large interlayer separations of about 13 ?. Magnetic investigations indicated that they all display intralayer antiferromagnetic interactions through the carboxylate bridges in the unusual skew-skew coordination mode but the bulk behaviors are quite different. The Co(II) compound, like most compounds containing similar M-O-C-O-M layers, shows no 3D magnetic ordering down to 2 K, while the Mn(II) and Fe(II) compounds exhibit spin-canted ordering, behaving as a weak ferromagnet (T(C) = 3.8 K) and a metamagnet (T(N) = 3.8 K, H(c) = 650 Oe), respectively. Spin-canted ordering is still a rarity in this series of materials. Magnetostructural comparisons with analogous compounds indicate that the occurrence of spin-canted ordering can be related to the uncommon skew-skew and anti-anti coordination modes of carboxylate bridges, which induce stronger antiferromagnetic interactions than the common syn-anti mode.     

Flexible mixed-spin Kagomé coordination polymers with reversible magnetism triggered by dehydration and rehydration

Two new two-dimensional (2D) heterometal coordination polymers [Cu(2)M(tzdc)(2)(H(2)O)(2)]·2H(2)O [M = Fe(2+) (1) or Mn(2+) (2); tzdc(3-) = 1,2,3-triazole-4,5-dicarboxylate] were assembled by using the tzdc(3-), Cu(2+), and Fe(2+)/Mn(2+) ions. Single-crystal X-ray analysis reveals that the two compounds consist of mixed-spin microporous Kagome? layers, which are packed into three-dimensional structures by hydrogen bonding and interlayer weak Cu···O interactions. When heated, they can release in a stepwise manner the uncoordinated and coordinated water molecules to produce dehydrated phases (1' and 2'), respectively, which are stable up to ～300 °C. The structures of 1' and 2' were determined by powder X-ray diffraction analysis, which reveals a change in the coordination sphere of Fe(2+)/Mn(2+) ions from an octahedron to an elongated 4+2 form, and a microporous-to-nonporous structural transformation involving intralayer wrinkling and interlayer superimposition. When the dehydrated samples are exposed to air, they can return to the hydrated phases quickly by adsorption of water molecules. Accordingly, a reversible change in magnetism between the ferrimagnetic character of the hydrated samples and the suppressed ferrimagnetic character of the dehydrated samples was found in this reversible dehydration and rehydration. These facts indicate these 2D heterometal coordination polymers are unique flexible 2D dynamic magnetic materials.     

Tricolor Luminescence Switching by Thermal and Mechanical Stimuli in the Crystal Polymorphs of Pyridyl‐substituted Fluorene

Stimuli‐responsive organic luminescence‐switching materials have attracted much attention for a decade. Most of the reported examples display a reversible two‐color luminescence switching, and multicolor‐switching materials remain extremely rare. Herein, we report a simple organic molecule, 4,4′‐(9,9‐dimethyl‐9H‐fluorene‐2,7‐diyl)dipyridine ( MFDP ), which exhibits three different crystal polymorphs ( V‐MFDP , B‐MFDP and G‐MFDP ) with different luminescent colors. Furthermore, the three crystal polymorphs show a reversible tricolor fluorescent switching from violet to blue and to green upon physical stimuli. The single‐crystal structures of the three polymorphs were obtained, and the results indicate that the stimuli‐responsive properties of the three polymorphs come from the different stacking modes induced by intermolecular interactions. The competition between weak π–π stacking and weak hydrogen bonding is the main reason for the the phase transformations among the three crystal polymorphs.     

Tuning the Interlayer Spacings in Dry Graphene Oxide Membranes via Ions

We show the experimental achievement of dry GO membranes with interlayer spacings in the range from 7.09 Å to 8.72 Å, tuned and fixed by salts. We found that the interlayer spacings were dominated by the anions or the groups with negative charges in between the GO membranes. Density functional theory (DFT) calculations reveal that the highly efficient tuning of the interlayer spacing in dry GO membranes is due to ion‐π interactions on the graphene sheets, together with the steric effects of anions in between the GO sheets. The findings are helpful for extending their potential applications including chemical sensors, nanomaterial devices preparation, chemical catalysis and synthesis, and gas separation.