Materials Chemistry and Crystal Growth

Materials chemistry and crystal growth are seen as closely related activities because the assessment and implementation of numerous physical properties are based on single crystals and epitaxial layers. The idea of a materials synthesis directed toward the investigation and application of physical solid-state properties is outlined by three examples: i) the supramolecular synthesis of polar molecular crystals, ii) a quest for optical materials for short wavelength generation, and iii) crystal growth and epitaxy of fluoride laser materials

Czochralski growth and spectroscopic investigations of Yb3+, La3+:Na2SO4(I) and Nd3+:Na2SO4(I)

Ln3+-stabilized Na2SO4 (phase I) single crystals were grown by the Czochralski method. Differential thermal analysis revealed the influence of the ionic radius of Ln3+ on the stabilization of Na2SO4(I). Distribution coefficients (∼0.8-1.1) were measured by the inductively coupled plasma optical emission spectroscopy method and x-ray fluorescence spectroscopy. Spectroscopic investigations yielded absorption cross sections of 0.6 × 10−20 cm2 (π-polarized, 928.5 nm) and 1.5 × 10−20 cm2 (π-polarized, 797.3 nm) for Yb3+, La3+:Na2SO4 and Nd3+:Na2SO4, respectively. Crystal growth of Gd3+-stabilized Na2SO4(I) provides an interesting new material for stimulated Raman scattering experiment

Universality behaviour for polarity formation in channel-type inclusion compounds

A statistical investigation based on a Markov chain theory of polarity formation applied to channel-type inclusion compounds loaded with both dipolar A-π-D and non-polar N-π-N (N: A or D) guests is presented. The key parameters effecting polarity formation are identified and their effects are explored. A number of paradoxes are set out and an attempt to explain the mechanisms behind them is made: dependence of macroscopic polarity on orientational selectivity induced by intermolecular interactions, tuning of polarity through (i) the concentration of non-polar guest and (ii) growth temperatur

Polarity formation by a higher order interaction Markov-like chain

Vector property generation is discussed for chain growth by higher order interactions. Because of a deterministic property evolution a state space approach was used. Although not strictly Markovian, the system shows ergodic properties and convergence for a large number of attachment steps. For reasonable interaction energies attributed to increasing order, the main extra contribution to polarity formation results from interactions up to next nearest neighbours. Nonlinear equations up to third order were solved by an iterative procedur

Symmetry and the polar state of condensed molecular matter

Polar molecular crystals seem to contradict a quantum mechanical statement, according to which no stationary state of a system features a permanent electrical polarization. By stationary we understand here an ensemble for which thermal averaging applies. In the language of statistical mechanics we have thus to ask for the thermal expectation value of the polarization in molecular crystals. Nucleation aggregates and growing crystal surfaces can provide a single degree of freedom for polar molecules required to average the polarization. By means of group theoretical reasoning and Monte Carlo simulations we show that such systems thermalize into a bi-polar state featuring zero bulk polarity. A two domain, i.e. bipolar state is obtained because boundaries are setting up opposing effective electrical fields. Described phenomena can be understood as a process of partial ergodicity-restoring. Experimentally, a bi-polar state of molecular crystals was demonstrated using phase sensitive second harmonic generation and scanning pyroelectric microscop

Observation of high-Tc superconductivity in inhomogeneous combinatorial ceramics

A single-sample synthesis concept based on multi-element ceramic samples can produce a variety of local products. When applied to cuprate superconductors (SC), statistical modelling predicts the occurrence of possible compounds in a concentration range of about 50 ppm. In samples with such low concentrations, determining which compositions are superconducting is a challenging task and requires local probes or separation techniques. Here, we report results from samples with seven components: BaO2, CaCO3, SrCO3, La2O3, PbCO3, ZrO2 and CuO oxides and carbonates, starting from different grain sizes. The reacted ceramics show different phases, particular grain growth, as well as variations in homogeneity and superconducting properties. High-Tc superconductivity up to 118 K was found. Powder x-ray diffraction (XRD) in combination with energy-dispersive spectroscopy (EDS), scanning transmission electron microscopy (STEM) can assign Pb1223 and (Sr,Ca,Ba)0.7-1.0CuO2 phases in inhomogeneous samples milled with 10 mm ball sizes. Rather uniform samples featuring strong grain growth were obtained with 3 mm ball sizes, resulting in Tc =70 K superconductivity of the La(Ba,Ca)2Cu3Ox based phase. Scanning SQUID microscopy (SSM) establishes locally formed superconducting areas at a level of a few microns in inhomogeneous superconducting particles captured by a magnetic separation technique. The present results demonstrate a new synthetic approach for attaining high-Tc superconductivity in compounds without Bi, Tl, Hg, or the need for high-pressure synthesis

Inclusion of tetramethylpyrazine in channels of the organic zeolite 2,4,6-tris(4-bromophenoxy)-1,3,5-triazine

2,4,6-tris(4-bromophenoxy)-1,3,5-triazine (BrPOT) features a channel size (11-12Å) allowing the inclusion of large guest molecules such as tetramethylpyrazine (TMPZ). TMPZ forms π-stacks (d: 3.5Å) along channels of BrPOT and shows rotational disorder for methyl positions. Co-inclusions of I2 resulted in a doped state where I2 molecules are oriented perpendicular to the channel axis with positional disorder as well. The particular orientation of I2 molecules is evident from the observed dichrois

Symmetry and the polar state of condensed molecular matter (Erratum)

Polar molecular crystals seem to contradict a quantum mechanical statement, according to which no stationary state of a system features a permanent electrical polarization. By stationary we understand here an ensemble for which thermal averaging applies. In the language of statistical mechanics we have thus to ask for the thermal expectation value of the polarization in molecular crystals. Nucleation aggregates and growing crystal surfaces can provide a single degree of freedom for polar molecules required to average the polarization. By means of group theoretical reasoning and Monte Carlo simulations we show that such systems thermalize into a bi-polar state featuring zero bulk polarity. A two domain, i.e. bipolar state is obtained because boundaries are setting up opposing effective electrical fields. Described phenomena can be understood as a process of partial ergodicity-restoring. Experimentally, a bi-polar state of molecular crystals was demonstrated using phase sensitive second harmonic generation and scanning pyroelectric microscop

Improved thermal stability of an organic zeolite by fluorination

The thermal stability of an organic zeolite material, namely 2,4,6-tris(4-bromo-3,5-difluorphenoxy)-1,3,5-triazin (Br-3,5-DFPOT), was improved by fluorination of 2,4,6-tris(4-bromophenoxy)-1,3,5-triazin (BrPOT). The open pore structure (van der Waals diameter of 10.5Å) of the modified zeolite was observed up to 110°C in comparison to 70°C for BrPOT. Nitrogen sorption at low temperature showed a type I isotherm and derived pore volumes thereof are in agreement with structural data. It was observed here that Br-3,5-DFPOT crystals preserving the open pore structure could only be obtained below a typical size of about 50μm. The improved thermal stability of the fluorinated system is attributed to an enhancement of the strength of the Br3-syntho

Novel Host-Guest Structures of 2,4,6- Tris (4-Halophenoxy)-1,3,5-Triazines(XPOT): Inclusion of C60 and Pyridine

The crystal structures of two halophenoxytriazine host-guest compounds are reported and discussed. They feature inclusion of C60 into cages of 2,4,6-tris(4-iodophenoxy)-1,3,5-triazine [IPOT, hexagonal, P63/m, a=16.367(2)Å, c=20.661(4)Å, V=4793.1(13)Å3, Z=2] and of pyridine6-clusters into cages of 2,4,6-tris(4-bromophenoxy)-1,3,5-triazine (BrPOT, rhombohedral, R $$\bar{3}$$ , a=15.5186(8)Å, c=39.521(3)Å, V=8242.7(8)Å3, Z=6). The stackings of the threefold symmetric layers of XPOT host molecules are different from each other and from those of all previously reported XPOT inclusion compounds (X: Cl, Br, I). Graphical Abstract: The new compounds IPOT3·C60 and BrPOT2·py3, represent new packing types in the family of threefold symmetric XPOT inclusion compounds (XPOT=2,4,6-tris(4-halophenoxy)-1,3,5-triazine; X=Cl, Br, I