二茂铁及其胺甲基类取代衍生物的紫外光解自由基的研究

本文用自旋捕捉-ESR技术研究了二茂戊铁、环二烯和胺甲基类取代二茂铁的紫外光解过程中的活泼自由基。结果表明,二茂铁光解初级过程中生成的自由基为(C_5H_5Fe)·和C_5H_5·,其衍生物光解则生成(C_5H_5Fe)·和RC_5H_4·,而(C_5H_5Fe)·还可以进一步分解给出C_5H_5和Fe。     

A review of the role of DSC analysis in the design of fluorozirconate glasses for fibre optic applications

The relatively poor thermal stability of fluorozirconate glasses is a major factor preventing the realisation of their true potential for fibre optic applications. A range of methods based on both isothermal and non-isothermal DSC techniques, which can be employed to evaluate the thermal stability of fluorozirconate glasses, are described. The relevance of these thermal stability criteria to the design of fluorozirconate compositions capable of yielding high quality optical fibres is discussed.     

New Photoluminescence Phenomena of Ge／SiO2 Glass Synthesized by Sol-gel Method

New Ge/SiO2 glasses have been synthesized by heating the GeO2/SiO2 dry gels under H2 gas at 700℃. The resulting fluorescence spectra show that this kind of Ge/SiO2 glasses emit strong photoluminescence at 392 nm (3.12 eV), medium strong photoluminescence at 600 nm (2.05 eV) and weak photoluminescence at 770 nm (1.60 eV) respectively. Possible photoluminescence mechanisms are also discussed based on the results of X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS).     

Structural integration of tellurium oxide into mixed-network-former glasses: connectivity distribution in the system NaPO(3)-TeO(2).

Sodium phosphate tellurite glasses in the system (NaPO(3))(x)(TeO(2))(1-) (x) were prepared and structurally characterized by thermal analysis, vibrational spectroscopy, X-ray photoelectron spectroscopy (XPS) and a variety of complementary solid-state nuclear magnetic resonance (NMR) techniques. Unlike the situation in other mixed-network-former glasses, the interaction between the two network formers tellurium oxide and phosphorus oxide produces no new structural units, and no sharing of the network modifier Na(2)O takes place. The glass structure can be regarded as a network of interlinked metaphosphate-type P(2) tetrahedral and TeO(4/2) antiprismatic units. The combined interpretation of the O 1s XPS data and the (31)P solid-state NMR spectra presents clear quantitative evidence for a nonstatistical connectivity distribution. Rather, the formation of homoatomic P--O--P and Te--O--Te linkages is favored over mixed P--O--Te connectivities. As a consequence of this chemical segregation effect, the spatial sodium distribution is not random, as also indicated by a detailed analysis of (31)P/(23)Na rotational echo double-resonance (REDOR) experiments.     

Reactivity of the 1,2-Diphenytethyl Radical in a Solvent Cage

The 1,2-diphcnylethyl radical and derivatives were generated from photolysis of tran-f-stilbene and its derivatives 1–13 with secondary amines as quenchers. The 1,2-diphenylelhyl radicals that escaped from the solvent cage were trapped by 2-methyl-2-nitrosopropane (MNP) and were detected by the HPLCEPR method. The yield of the spin adduct is greater for tertiary amines. The smaller yields of the spin adduct formed from secondary amines are ascribed to greater reactivities of the 1,2-diphenylethyl and dialkylamino radicals within the solvent cage.     

Multifunctionality in spin crossover materials

One of the most important trends in the spin crossover (SCO) field is focused on the synthesis of new molecule-based functional materials in which the SCO properties may be combined with other physical or chemical properties in a synergic fashion. The current stage of investigations regarding interplay and synergic effects between SCO, magnetic coupling, liquid crystalline properties, host-guest interactions, non-linear optical properties, electrical conductivity, and ligand isomerization is highlighted and discussed.     

The spherical limit forn-vector correlations

We investigate then limit of then-vector model single-spin and pairspin correlation functions. In this limit we show that the correlation functions become those of the corresponding spherical model.     

Synthesis, crystal structure and magnetic property of a new 1D molecular material [1-(4′-chlorobenzyl)-4-aminopyridinium](+) bis(maleonitriledithiolato)nickel(-)

A new ion-pair complex, [1-(4′-chlorobenzyl)-4-aminopyridinium](+)bis(maleonitrile-dithiolato)nickel(−),[ClbzPyNH₂][Ni(mnt)₂] (1), has been prepared and characterized. X-ray single crystal structure conforms that the Ni(mnt)₂⁻ anions and [ClbzPyNH₂]⁺ cations of 1 form completely segregated uniform stacking columns with the Ni?Ni distance 3.944 Å in the Ni(mnt)₂⁻ stacking column. The temperature dependence of the magnetic susceptibility reveals that 1 undergoes a magnetic transition, and exhibits ferromagnetic interaction in the high-temperature phase and spin gap system in the low-temperature phase.     

Anharmonicity and fragility in lithium borate glasses

Since the physical properties of lithium borate glasses xLi₂O-(1-x)B₂O₃ (0<x< 0.28) vary over a wide range with the composition, this binary system is particularly suitable for studying the relationship between vibrational anharmonicity and fragility. The density, the linear expansion coefficient, the longitudinal and transverse ultrasonic velocities and their respective temperature coefficients of the velocities are measured, from which the vibrational anharmonicity in lithium borate glasses is evaluated with the help of the Grüneisen parameter at the Debye cut-off frequency and the Anderson-Grüneisen parameter: these two parameters plotted vs. composition have the same characteristics with minima at x≈0.08. The fragility is evaluated from the temperature width of the glass transition; the fragility also shows a minimum at x≈0.08. The presence of minima at x≈0.08 is ascribable to the fact that the crosslinking density between six-membered rings in the glass reaches a maximum at this composition. We show that the anharmonic parameters strongly correlate with the fragility metrics. This revised version was published online in August 2006 with corrections to the Cover Date.