Cooperative spin transition in the two-dimensional coordination polymer [Fe(4,4'-bipyridine)2(NCX)2]·4CHCl3 (X = S, Se)

Two new isostructural two-dimensional (2D) coordination polymers exhibiting spin crossover (SCO) behavior of formulation [Fe(4,4'-bipy)(2)(NCX)(2)]·4CHCl(3) (4,4'-bipy = 4,4'-bipyridine; X = S [1·4CHCl(3)], Se [2·4CHCl(3)]) have been synthesized and characterized, and both undergo cooperative spin transitions (ST). For 1·4CHCl(3) the ST takes place in two steps with critical temperatures of T(c1)(down) = 143.1 K, T(c2)(down) = 91.2 K, T(c1)(up) = 150.7 K, and T(c2)(up) = 112.2 K. 2·4CHCl(3) displays half ST characterized by T(c)(down) = 161.7 K and T(c)(up) = 168.3 K. The average enthalpy and entropy variations and cooperativity parameters associated with the ST have been estimated to be ΔH(1)(av) = 5.18 kJ mol(-1), ΔS(1)(av) = 35 J K(-1) mol(-1), and Γ(1) = 2.8 kJ mol(-1) and ΔH(2)(av) = 3.55 kJ mol(-1), ΔS(2)(av) = 35 J K(-1) mol(-1), and Γ(2) = 2.6 kJ mol(-1) for 1·4CHCl(3), and ΔH(av) = 6.25 kJ mol(-1), ΔS(av) = 38.1 J K(-1) mol(-1), and Γ = 3.2 kJ mol(-1) for 2·4CHCl(3). At T > [T(c1) (1·4CHCl(3)); T(c) (2·4CHCl(3))], both compounds are in the space group P2/c while at T < [T(c1) (1·4CHCl(3)); T(c) (2·4CHCl(3))] they change to the C2/c space group and display an ordered checkerboard-like arrangement of iron(II) sites where the high- and low-spin states coexist at 50%.     

Critical phenomenon of nonaqueous microemulsion (AOT/DMA/decane)

The critical phenomenon of nonaqueous microemulsion was studied for the first time. The coexistence curves of (T,n), (T,phi), and (T,psi) (n and phi are refractive index and volume fraction, respectively; psi is defined as psi=phi/[phi+phi(c)(1-phi)/(1-phi(c))]) for a ternary microemulsion [phi (AOT-DMA)+(1-phi) decane] at constant pressure and a constant molar ratio (omega=2.86) of DMA to AOT have been determined within about 7 K from the critical temperature T(c) by measurements of refractive index. The critical exponent beta has been deduced from (T,n), (T,phi), and (T,psi) coexistence curves within 1 K below T(c). They all were 0.329+/-0.005 and were consistent with the 3D Ising value. The experimental results in a temperature range of (T(c)-T)<7 K also have been analyzed to obtain critical amplitudes and the Wegner correction terms, to examine the diameters of the coexistence curves.     

Van der Waals supercritical fluid: exact formulas for special lines

In the framework of the van der Waals model, analytical expressions for the locus of extrema (ridges) for heat capacity, thermal expansion coefficient, compressibility, density fluctuation, and sound velocity in the supercritical region have been obtained. It was found that the ridges for different thermodynamic values virtually merge into single Widom line only at T < 1.07T(c), P < 1.25P(c) and become smeared at T < 2T(c), P < 5P(c), where T(c) and P(c) are the critical temperature and pressure. The behavior of the Batschinski lines and the pseudo-Gruneisen parameter γ of a van der Waals fluid were analyzed. In the critical point, the van der Waals fluid has γ = 8/3, corresponding to a soft sphere particle system with exponent n = 14.     

New organic superconductors beta-(BDA-TTP)2X [BDA-TTP + 2,5-bis(1,3-dithian-2ylidene)-1,3,4,6-tetrathiapentalene; X(-) = SbF6(-), AsF6(-), and PF6(-)].

The synthesis, electrochemical properties, and molecular structure of a new pi-electron donor, 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP), is described. In contrast to the hitherto-known tetrachalcogenafulvalene pi-donors providing organic superconductors, this donor contains only the bis-fused 1,3-dithiole-2-ylidene unit as a pi-electron system, yet produces a series of ambient-pressure superconductors beta-(BDA-TTP)2X [X = SbF6 (magnetic T(c) = 6.9 K, resistive T(c) = 7.5 K), AsF6 (magnetic T(c) = 5.9 K, resistive T(c) = 5.8 K), and PF6 (magnetic T(c) = 5.9 K)], which are isostructural. The values of the intermolecular overlap integrals calculated on the donor layers of these superconductors suggest a two-dimensional (2D) electronic structure with loose donor packing. Tight-binding band calculations also indicate that these superconductors have the 2D band dispersion relations and closed Fermi surfaces.     

Effect of water on glass transition in starch/sucrose matrices investigated through positron annihilation lifetime spectroscopy: a new approach

Glass transition is studied through positron annihilation lifetime spectroscopy (PALS) in maize starch matrices containing 10 (batch STS10) and 20 (STS20) w/w% sucrose, as a function of temperature (T) and water content (c(w)). To circumvent important losses of water upon heating while recording the PALS spectra, a new method is developed: instead of a series of measurements of τ(3), the triplet positronium lifetime, at different T, the latter is kept constant and the series relates to c(w), which is left to decrease at a constant rate. Similarly to the changes in τ(3) with T, the τ(3)vs. c(w) plots obtained show a smooth linear increase until a break, denoting the occurrence of glass transition, followed by a sharper increase. The gradients appear to be independent of T. The variation of the glass transition temperature, T(g), with c(w) shows a broad sigmoid with a large linear central part; as expected from the plasticising effect of sucrose, the plot for STS20 lies some 10 K below that for STS10. Results from differential scanning calorimetry for STS20 yield T(g) values some 15 K higher than from PALS. On the basis of the general shape of the τ(3)vs. T variations, a general equation is set for τ(3)(T, c(w)), leading one to expect a similar shape for τ(3)vs. c(w), as experimentally observed.     

Tuning the critical temperature of cuprate superconductor films with self-assembled organic layers

Control over the T(c) value of high-T(c) superconductors by self-assembled monolayers is demonstrated (T(c) = critical temperature). Molecular control was achieved by adsorption of polar molecules on the superconductor surface (see scheme) that change its carrier concentration through charge transport or light-induced polarization.     

Size dependence of second-order optical nonlinearity of CdS nanoparticles studied by hyper-Rayleigh scattering

Rutile TiO(2) particles were partly dissolved into aqueous solutions of H(2)SO(4), and the Ti(4+) ions were reprecipitated by adding NH(3) aq. Rutile-anatase coupled TiO(2) particles were prepared by heating the solid recovered after centrifugation of the suspension. The content of anatase (c(A), wt%) could be controlled arbitrarily by changing the dissolved amount of rutile. The photocatalytic activity for the gas-phase oxidation of acetaldehyde was evaluated. The first-order rate constant, k, strongly depended on both c(A) and heating temperature (T(c)), increasing with an increase in T(c) at T(c)相似文献   

Precise control and consecutive modulation of spin transition temperature using chemical migration in porous coordination polymers

Precise control of spin transition temperature (T(c)) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[Pt(II)(CN)(4)]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T(c)(up) = 304 K and T(c)(down) = 284 K) and its iodine adduct {Fe(pz)[Pt(II/IV)(CN)(4)(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt(II), raised the T(c) by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe(pz)[Pt(CN)(4)(I)(n)]} (1-In; n = 0.0-1.0), which resulted in consecutive modulation of T(c) in the range 300-400 K while maintaining the hysteresis width. Furthermore, it was demonstrated that iodine migration in the solid mixture was triggered by the spin transition of 1-I. The magnetically bistable porous framework decorating guest interactive open-metal-site in the pore surface makes it possible to modulate T(c) ad arbitrium through unique postsynthetic method using iodine migration.     

Control of structure formation in phase-separating systems

In this paper, we study the evolution of phase-separating binary mixtures which are subjected to alternate cooling and heating cycles. An initially homogeneous mixture is rapidly quenched to a temperature T(1)T(c). These cycles are repeated to create a domain morphology with multiple length scales, i.e., the structure factor is characterized by multiple peaks. For phase separation in d = 2 systems, we present numerical and analytical results for the emergence and growth of this multiple-scale morphology.     

Superconductivity in LaT(M)BN and La3T(M2)B2N3 (T(M) = transition metal) synthesized under high pressure

Various layered boronitrides (LaN)(n)(T(M2)B(2)) (T(M) = transition metal; n = 2, 3) have been prepared using a high-pressure synthesis technique in which an inverse α-PbO-type T(M2)B(2) layer is separated by two or three rock salt-type LaN layers and these layers are connected through linear (BN) units. The electronic states of the distinguishing (BN) unit and intermediate rock salt-type LaN layer are discussed on the basis of density functional theory calculations. Bulk superconductivity has been found in LaNiBN (T(c) ≈ 4.1 K), CaNiBN (T(c) ≈ 2.2 K), and LaPtBN (T(c) ≈ 6.7 K), where the Fermi level E(F) is located in the bands composed of the T(M)(d)-B(2p) antibonding state and the main T(M)(d) band resides well below E(F). The non-superconductive T(M)-based compounds exhibit Pauli paramagnetic behavior, in which the highly itinerant nature of the electrons caused by strong T(M)(d)-B(2p) covalent bonding suppresses the long-range magnetic ordering.     

Ferroelectricity and pressure-induced phenomena driven by neutral ionic valence instability of acid-base supramolecules

Supramolecular ferroelectric cocrystals of phenazine (Phz) with chloranilic acid (H(2)ca), bromanilic acid (H(2)ba), and fluoranilic acid (H(2)fa) have been characterized by the interplay between their structural transformations and solid-state acid-base (proton transfer) reactions. At ambient pressure, the Phz-H(2)ca, Phz-H(2)ba, and their deuterated crystals exhibit incomplete proton displacement, which transforms the neutral molecules into semi-ionic at low temperatures below the Curie point (T(c)(IC) < T < T(c)(I)). For the cocrystal of the less acidic H(2)fa, the ferroelectric phase is induced only by applying hydrostatic pressure above ~0.6 GPa. According to the combined studies of temperature-dependent dielectric permittivity and synchrotron X-ray diffraction, it was proved that the ferroelectric (FE-I) phase is always accompanied at lower temperatures by successive phase transitions to the lattice modulated phases with incommensurate periodicities (IC phase, T(c)(II) < T < T(c)(IC)) and with commensurate (2- or 3-fold) periodicities (FE-II or FE-III phase, T < T(c)(II)). Whereas the ground-state structures at ambient pressure are different from one another among the Phz-H(2)ca (FE-II form), Phz-H(2)ba (FE-III form), and Phz-H(2)fa (paraelectric form), their systematic changes under pressure depict a universal pressure-temperature phase diagram. The possible origins of structural changes are assigned to the valence instability and the frustrated Coulomb interactions that induce the charge disproportionation (coexisting neutral ionic) states with the staging spatial orders.     

Cloud point temperature of polyoxyethylene-type nonionic surfactants and their mixtures

The cloud point temperature, T(c), was investigated for aqueous solutions of poly(oxyethylene) alkyl ethers, C(n)E(m), and their mixtures. The experimental T(c)'s for single surfactant systems were analyzed according to the Flory-Huggins model for cloud point phenomenon, and the enthalpy and the entropy changes associated with the process of the separation of micellar solution into pure water and pure surfactant were estimated. It was found that the enthalpy-entropy compensation relationship holds for this process. The Flory-Huggins model was extended to the binary surfactant mixtures, and the expression of T(c) as a function of the composition was derived assuming the regular solution for mixed micelles. The experimental results of T(c) obtained for mixtures of C(n)E(m) were well reproduced by the model calculation. Discussion is given concerning the interaction parameters of different surfactant species in mixed micelles determined by this model calculation.     

Landau theory description of observed isotropic to anisotropic phase transition in mixed clay gels

A characteristic new cooperative dehydration transition, in 1:1 Laponite-MMT cogel, was observed at T(c) ≈ 60 °C, a temperature at which the storage modulus (G(')) and depolarization ratio (D(p)) showed sharp increase, and the isotropic cogel turned into an anisotropic one. The dehydration dynamics could be described through power-law relations: G(') ～ (T(c)-T)(-γ) and D(p) ～ (T(c)-T)(-β) with γ ≈ β = 0.40 ± 0.05. The x-ray diffraction data revealed that the crystallite size decreased from 17 nm (at 20 °C) to 10 nm (at 80 °C) implying loss of free and inter-planar water. When this cogel was spontaneously cooled below T(c), it exhibited much larger storage modulii values which implied the existence of several metastable states in this system. This phase transition could be modeled through Landau theory, where the depolarization ratio was used as experimental order parameter (ψ). This parameter was found to scale with temperature, as ψ ～ (T(c)-T)(-α), with power-law exponent α = 0.40 ± 0.05; interestingly, we found α ≈ β ≈ γ.     

Static and dynamic critical behavior of a symmetrical binary fluid: a computer simulation

A symmetrical binary, A+B Lennard-Jones mixture is studied by a combination of semi-grand-canonical Monte Carlo (SGMC) and molecular dynamics (MD) methods near a liquid-liquid critical temperature T(c). Choosing equal chemical potentials for the two species, the SGMC switches identities (A-->B-->A) to generate well-equilibrated configurations of the system on the coexistence curve for TT(c). A finite-size scaling analysis of the concentration susceptibility above T(c) and of the order parameter below T(c) is performed, varying the number of particles from N=400 to 12 800. The data are fully compatible with the expected critical exponents of the three-dimensional Ising universality class. The equilibrium configurations from the SGMC runs are used as initial states for microcanonical MD runs, from which transport coefficients are extracted. Self-diffusion coefficients are obtained from the Einstein relation, while the interdiffusion coefficient and the shear viscosity are estimated from Green-Kubo expressions. As expected, the self-diffusion constant does not display a detectable critical anomaly. With appropriate finite-size scaling analysis, we show that the simulation data for the shear viscosity and the mutual diffusion constant are quite consistent both with the theoretically predicted behavior, including the critical exponents and amplitudes, and with the most accurate experimental evidence.     

The Nowotny chimney ladder phases: following the c(pseudo) clue toward an explanation of the 14 electron rule

We account for two empirical rules of the Nowotny chimney ladder phases (NCLs, intermetallic compounds of the form T(t)E(m); T, groups 4-9; E, groups 13-15). The first rule is that for late transition metal NCLs the total number of valence electrons per T atom is 14. The second is the appearance of a pseudoperiodicity with a spacing, c(pseudo), which is directly related to the stoichiometry, T(t)E(m), by (2t - m) c(pseudo)= c. Both rules are accounted for by viewing the NCLs as twinned structures constructed from blocks of the parent compound, RuGa(2) of thickness c(pseudo)/2, with the successive layers rotated relative to each other by 90 degrees. Sterically encumbered E atoms are then deleted at the interfaces between layers, followed by relaxation.     

Dual types of spherulites in poly(octamethylene terephthalate) confined in thin-film growth

Spherulite morphology and growth kinetics of poly(octamethylene terephthalate) (POT), cast on single-side glass or confined between two slides in thin-film forms, were characterized using polarized versus nonpolarized optical microscopy, scanning electron microscopy (SEM), and wide-angle X-ray (WAXD) analysis. POT can simultaneously display solely one type of spherulite or dual types of spherulites (double-ring-banded and ringless ones), depending on T c or T max imposed. Fractions of these two types depend on T c when quenched from a fixed T max = 160 degrees C. At lower T c's, POT exhibits higher crystallization rates leading to higher fractions of ringless spherulites; at higher T c's, POT exhibits lower crystallization rates leading to ring-banded spherulites. At intermediate to high T c's where the growth kinetics of POT could be monitored, the ring-band type dominates and the fraction of ringless spherulites is insignificantly small. Both ringless and ring-banded spherulites can be seen in regime III ( T c = 70-110 degrees C), with fractions of ringless type of spherulites decreasing with temperature. Thus, growth kinetics for POT was mainly focused on the regime of ring-banded spherulites. In regime III, the ring-band pattern is more orderly concentric with smaller inter-ring spacing (1-2 mum) for lower T c's but intermediately larger spacing (3-5 mum) for higher T c's. The orderly lamellar orientation in the ring-bands in contrast with the inter-ring valley region is discussed. In regime II (115 degrees C and above), the ring-band pattern is first distorted to highly zigzag irregularity at higher T c's and then eventually disappears at extremely high T c, with the lamellar crystals eventually turning dendritic with no rings. Apparently, the types of spherulites in polymers are more influenced by the growth rates as determined by T c and slightly less by T max, but not by the substrate surface nucleation.     

Temperature and composition dependence of the Soret coefficient in Lennard-Jones mixtures presenting evaporation/condensation phase transition

The thermodiffusive behavior of a Lennard-Jones binary mixture has been studied by using nonequilibrium molecular dynamics. In particular, the dependence of the Soret coefficient, S(T), on the temperature and composition has been investigated, exploring a wide range of temperatures from 1000 K to the condensation temperature of the mixture. In a previous paper the dependence of S(T) on the temperature and the composition was studied for Lennard-Jones binary mixtures presenting mixing/demixing (consolute) phase transition, and the results allowed the formulation of a very simple expression with the computed values of S(T) in the one phase region outside the critical region closely fitted by the function [T - T(c)(x(1))](-1), with T(c)(x(1)) the demixing temperature of the mixture under study. The results of the present work show that the same expression of S(T) can be found for the one phase region outside the evaporation/condensation region but now with T(c) representing the condensation temperature of the mixture under study.     

Syntheses, structures, and physical properties of LnAsTe (Ln = La, Pr, Sm, Gd, Dy, Er)

Six rare-earth arsenic tellurides have been synthesized by the reactions of the rare-earth elements (Ln) with As and Te at 1123 K. LaAsTe (a = 7.8354(11) A, b = 4.1721(6) A, c = 10.2985(14) A, T = 153 K), PrAsTe (a = 7.728(2) A, b = 4.1200(11) A, c = 10.137(3) A, T = 153 K), SmAsTe (a = 7.6180(16) A, b = 4.0821(9) A, c = 9.991(2) A, T = 153 K), GdAsTe (a = 7.5611(15) A, b = 4.0510(8) A, c = 9.920(2) A, T = 153 K), DyAsTe (a = 7.4951(13) A, b = 4.0246(7) A, c = 9.8288(17) A, T = 153 K), and ErAsTe (a = 7.4478(1) A, b = 4.0078(1) A, c = 9.7552(2) A, T = 153 K) crystallize with four formula units in the orthorhombic space group D2h16-Pnma. These compounds are isostructural and belong to the beta-ZrSb2 structure type. In each compound, the Ln atoms are coordinated by a tricapped trigonal prism of four As atoms and five Te atoms. The entire three-dimensional structure is built up by the motif of the LnAs4Te5 tricapped trigonal prisms. Infinite nonalternating zigzag As chains are found along the b axis, with As-As distances in these compounds ranging from 2.5915(5) to 2.6350(9) A. Conductivity measurements in the direction of these As chains indicate that PrAsTe is metallic whereas SmAsTe and DyAsTe are weakly metallic. Antiferromagnetic transitions occur in SmAsTe and DyAsTe at 3 and 9 K, respectively. DyAsTe above 9 K follows the Curie-Weiss law.