NMR Spectra of polyimides: Interpretation and local chain motion study

Three kinds of high-performance polyimides 1 (poly(ketone-imide) PKI), 2 (poly(ether-imide) PEI) and 3 (poly(oxy-imide) POI) were studied using nuclear magnetic resonance (NMR). The NMR spectra of the polyimides were assigned according to the comprehensive consideration of the substitution effect of different substituting groups, viz. distortionless enhancement by polarization transfer (DEPT), no nuclear Overhauser effect (NNE), analysis of relaxation time, and two-dimensional correlated spectroscopy (COSY) techniques. The structural units of these three polyimides were determined. Carbon-13 and proton relaxation times for PEI and PKI were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (JS model) and anisotropic group rotation such as phenyl group rotation and methyl group rotation. Correlation times for the main-chain motion are in the tens of picosecond range which indicates the high flexibility of polyimide chains. Correlation times for phenyl group and methyl group rotations are more than 1 order of magnitude lower and approximately 1 order of magnitude higher than that of the main chain, respectively.

SYNTHESIS OF A NEW CHIRAL LIQUID-CRYSTAL WITH SCHIFF-BASE GROUP AND INVESTIGATION OF TEMPERATURE-DEPENDING FTIR SPECTRA

A new chiral liquid crystal with Schiff base group has been prepared, The structure of liquid crystal was confirmed by elementary analyses and H-1 NMR. Its phase transition was investigated by polarized optical microscope, DSC and temperature-depending FTIR spectra. The results showed that the chiral Schiff base showed monotropic phases behavior in certain temperature range, the phase sequence is I-N-*-S-B-S-G-K on the cooling sequence.

OPTICAL AND STRUCTURAL INVESTIGATION OF KMGLA(PO4)(2) PHOSPHATE DOPED WITH EUROPIUM

A new compound KMgLa(PO4)(2), isotypic with monoclinic LaPO4, is reported. Its cell parameters have been determined from X-ray powder diffraction data. Crystallization occurs in the monoclinic space group P2(1)/n (No. 14) with a = 6.839(3) Angstrom, b = 7.066(1) Angstrom, c = 6.523(3) Angstrom, beta = 103.42(4)degrees, and Z = 2. It was found that the KMgLa(PO4)(2) phase was isostructural with monoclinic LaPO4. The difference between them was that half of the La atoms in LaPO4 were couplingly substituted with the same amount of Mg and K atoms. This isomorphous substitution was confirmed by IR and Eu3+-doped excitation and emission spectra and by elemental analysis of single crystals. The spectroscopic data were compared with those of LaPO4:Eu3+. (C) 1995 Academic Press, Inc.

PREPARATION, CRYSTAL-STRUCTURE, AND VIBRATIONAL-SPECTRA OF PEROVSKITE-TYPE MIXED OXIDES LAM(Y)M'(1-Y)O(3) (M,M'=MN, FE, CO)

Three series of samples LaMnyCo1-yO3+/-lambda, LaFeyMn1-yO3+/-lambda, and LaFeyCo1-yO3+/-lambda (y = 0.0 to 1.0) with Perovskite structure were prepared by an explosion method different from the generally used ceramic techniques. The variation of crystal

CRYSTAL-STRUCTURE AND INFRARED-SPECTRA OF A LANTHANUM COORDINATION COMPOUND WITH GLYCINE, ([LA(GLY)S-CENTER-DOT-2H2O]CENTER-DOT(CLO4)3)N

A lanthanum coordination compound with glycine {[La(Gly)3.2H2O].(ClO4)3}n (Gly = NH+ 3-CH2-COO-) was synthesized and obtained in the form of single crystals. Its X-ray crystal structure has been determined and the IR spectrum has been studied. Crystallo

CRYSTAL-STRUCTURES AND MOSSBAUER-SPECTRA OF LAFE1-XMNXO3 AND LAFE1-XCOXO3 (X=0 TO 0.9)

The crystal structures and Mossbauer spectra of various mixed oxides LaFe1-xMnxO3 and LaFe1-xCoxO3 (x = 0 to 0.9) are determined and measured at room temperature. The results indicate that the crystal structure of both the La-Fe-Mn-O and the La-Fe-Co-O sy

A STUDY OF CHARGE SEPARATION AND ELECTRON-CAPTURE INDUCED DECOMPOSITION SPECTRA OF PHENYLENEDIAMINE ISOMERS

The structures and decomposition reactions of doubly charged phenylenediamines were studied by means of charge separation (CS) and electron capture induced decomposition (ECID) spectra. The deisomerization of the three isomers is prior to the metastable d

LUMINESCENCE AND ENERGY-TRANSFER IN GDP5O14-EU3+,SM3+ SINGLE-CRYSTALS

In this paper we report on the luminescence and energy transfer in GdP4O14:Eu3+,Sm3+ (GdPP:Eu,Sm) in single crystals grown by the hydrothermal method. The room temperature excitation, emission, absorption and IR spectra of the crystals have been measured and analysed. The energy transfer from Gd3+ and Sm3+ to Eu3+ ions in GPP:Eu,Sm crystals is also discussed.

THE VALENCY AND SPECTRA OF SAMARIUM IONS IN MF(2)-MGF2 (M=CA, SR, BA)

The phosphors MMgF(4)(M = Ca, Sr, Ba) doped with samarium ions are synthesized in different atmospheres using solid phase reaction at high temperature. Samarium has been first stabilized in the divalent state in SrMgF4 and BaMgF4 matrices. Effects of matrices on the valent state of samarium ions are briefly discussed.

INFRARED-SPECTRA OF DIMETHYLPHOSPHATE LANTHANIDE COMPLEXES

The infrared spectra of the crystalline solid samples of rare earth(III) dimethylphosphates Ln(DMP)3 (Ln = La, Ce, Nd) in the range 4000-100 cm-1 are discussed. It is shown that the spectra may be treated by dividing Ln(DMP)3 into two parts, an OP(OCH3)2O bridge and a LnO6 distortion octahedron. The absorption bands above 500 cm-1 may be clearly assigned. However, vibrational assignments in the far-infrared region are tentative.

X-RAY PHOTOELECTRON-SPECTRA OF SOME BIOINORGANIC COMPLEXES OF THE RARE-EARTHS WITH N-ACETYLALANINE

X-Ray photoelectron spectra of some bioinorganic complexes of La, Ce, PT, Nd, Sm and Eu with N-acetylalanine have been measured and the 3d5/2 and 3d3/2 main peaks and their satellites have also been assigned. ne spin-orbit splitting between the 3d5/2 and 3d3/2 core-level of the rare earth ion in these complexes becomes slightly larger than that of the free rare earth atom due to the effect of the crystal field. The satellite for the 3d main peaks of La in the solid state complex are in higher binding energy region and may be attributable to the L --> 4f charge-transfer shake-up process. The satellites for the 3d main peaks of Ce, Pr, Nd, Sm and Eu are in the lower binding energy region and may be attributable to the 4f --> L charge-transfer shake-down process.

PHOTOELECTRON-SPECTRA OF COMPLEXES OF NA AND LA WITH N-ACETYLALANINE AND N-ACETYLVALINE

X-ray photoelectron spectra of the bioinorganic complexes of Na and La with N-acetylalanine and N-acetylvaline have been measured. It has been found that the spectra of the O 1s core level in the complexes of Na with these amino acids are very different from those in the complexes of La with the same amino acids. The results indicate that in the complexes of La with N-acetylalanine and N-acetylvaline, both the oxygen atoms from the carboxyl group and the oxygen atoms from the carbonyl group of the amino acids will directly coordinate to the La ion, whereas only the oxygen atoms from the carboxyl group of the amino acids can directly coordinate to the Na ion in the complexes of Na with N-acetylalanine and N-acetylvaline.

PHOTOELECTRON-SPECTRA OF VARIOUS CORE LEVELS IN SOME RARE-EARTH N-ACETYLVALINE BIOINORGANIC COMPLEXES

X-ray photoelectron spectra of some bioinorganic complexes of La, Pr, Nd, Sm, and Gd with N-acetylvaline have-been measured. The complex formation does not give any detectable influence on the binding energy of the N 1s peak in the amino group, but has some appreciable effect on the binding energy of the C 1s peak and the O 1s peak in the carboxyl and carbonyl group of the biological ligand. The spin-orbit splitting between the 3d5/2 and 3d3/2 core level of the rare earth ion in these bioinorganic complexes also becomes slightly larger than that of the free rare earth atom due to the effect of the crystal field from the biological ligands.

THE INVESTIGATION ON THE EMISSION CENTERS AND SUBSTITUTING SITES IN KMGF3-CE3+

With the method of high temperature solid state reaction and stockbarger, we synthesized a series of powder phosphors of KMgF3-Ce3+, KMg1-alphaMalphaF3-Ce3+(M = Be2+, Ca2+) and the single crystal of KMgF3-Ce3+. We tested their excitation and emission spectra, found two emission centers in KMgF3-Ce3+ and demonstrated that they resulted from different charge compensating ways. By the structural analysis on KMgF3-Ce-3+ from a four-cycle diffractometer and spectral analysis on KMg1-alphaMalphaF3-Ce3+(M = Be2+, Ca2+), we deduced that Ce3+ ion only.substituted K+ site in KMgF3.