Triarylborane-Appended New Triad and Tetrad: Chromogenic and Fluorogenic Anion Recognition

Facile synthesis of triad 3 and tetrad 4 incorporating -B(Mes)(2) (Mes = mesityl (2,4,6-trimethylphenyl)), boron dipyrromethene (BODIPY), and triphenylamine is reported. Introduction of two dissimilar acceptors (triarylborane and BODIPY) on a single donor resulted in two distinct intramolecular charge transfer processes (amine-to-borane and amine-to-BODIPY). The absorption and emission properties of the new triad and tetrad are highly dependent on individual building units. The nature of electronic communication among the individual fluorophore units has been comprehensively investigated and compared with building units. Compounds 3 and 4 showed chromogenic and fluorogenic responses for small anions such as fluoride and cyanide.

New 4-(2-(4-alkoxyphenyl)-6-methoxypyridin-4-yl) benzonitriles: synthesis, liquid crystalline behavior and photo physical properties

A new series of luminescent 4-(2-(4-alkoxyphenyl)-6-methoxypyridin-4-yl) benzonitriles containing three ring systems, viz. methoxy pyridine, benzonitrile and alkoxy benzene with variable alkoxy chain length, with bent-core structures were synthesized as potential mesogens and characterized by spectral techniques. Their liquid crystalline behavior was investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and variable temperature powder X-ray diffraction (PXRD) measurements. The study reveals that compounds with shorter chain lengths i.e. m = 4] exclusively exhibit the nematic phase while compounds with longer chain lengths i.e. m = 6-14 (only even)] show predominantly the orthorhombic columnar phase. Single crystal X-ray analysis of 4-(2-(4-butyloxy/octyloxyphenyl)-6-methoxypyridin-4-yl) benzonitriles reveals that they possess slightly non-planar unsymmetrical bent structures and their molecular packing consists of nonconventional H-bond interactions; it also explains the observed liquid crystalline phase. An optical study indicates that the title compounds are good blue emitting materials showing absorption and emission bands in the range 335-345 nm and 415-460 nm, respectively. An electrochemical study of 4-(2-(4-octyloxyphenyl)-6-methoxypyridin-4-yl) benzonitrile shows a band gap of 1.89 eV with HOMO and LUMO energy levels of -5.06 and -3.17 eV, respectively. Also, density functional theory (DFT) calculations confirm its optimized geometry, electronic absorption and frontier molecular orbital distributions.

Ultrafast Chemical Dynamics in Time Domain Through Fluorescence Spectroscopy

While absorption and emission spectroscopy have always been used to detect and characterize molecules and molecular complexes, the availability of ultrashort laser pulses and associated computer-aided optical detection techniques allowed study of chemical processes directly in the time domain at unprecedented time scales, through appearance and disappearance of fluorescence from participating chemical species. Application of such techniques to chemical dynamics in liquids, where many processes occur with picosecond and femtosecond time scales lead to the discovery of a host of new phenomena that in turn led to the development of many new theories. Experiment and theory together provided new and valuable insight into many fundamental chemical processes, like isomerization dynamics, electron and proton transfer reactions, vibrational energy and phase relaxation, photosynthesis, to name just a few. In this article, we shall review a few of such discoveries in attempt to provide a glimpse of the fascinating research employing fluorescence spectroscopy that changed the field of chemical dynamics forever.

InGaN/GaN LEDs grown on Si(111): Dependence of device performance on threading dislocation density and emission wavelength

We demonstrate the growth of crack-free blue and greenemitting LED structures grown on 2-inch and 6-inch Si(111) substrates by metalorganic vapour phase epitaxy (MOVPE), using AlN nucleation layers and AlGaN buffer layers for stress management. LED device performance and its dependence on threading dislocation (TD) density and emission wavelength were studied. Despite the inherently low light extraction efficiency, an output power of 1.2 mW at 50 mA was measured from a 500 μm square planar device, emitting at 455 nm. The light output decreases dramatically as the emission wavelength increases from 455 nm to 510 nm. For LED devices emitting at similar wavelength, the light output was more than doubled when the TD density was reduced from 5×1 09 cm-2 to 2×109 cm-2. Our results clearly show that high TD density is detrimental to the overall light output, highlighting the need for further TD reduction for structures grown on Si. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

Dislocation nucleation and emission from crack-tip

The problems of dislocation nucleation and emission from a crack tip are analysed based on Peierls model. The concept adopted here is essentially the same as that proposed by Rice. A slight modification is introduced here to identify the pure linear elastic response of material. A set of new governing equations is developed, which is different from that used by Beltz and Rice. The stress field and the dislocation density field can be expressed as the first and second Chebyshev polynomial series respectively. Then the opening and slip displacements can be expanded as the trigonometric series. The Newton-Raphson Method is used to solve a set of nonlinear algebraic equations. The new governing equations allow us to extend the analyses to the case of dislocation emission. The calculation results for pure shearing, pure tension and combined tension and shear loading are given in detail.

Two-dimensional short surface-waves of an oscillating cylinder with arbitrary shape of cross-section

The 2-D short surface waves produced by a partially submerged cylinder which performsarbitrary oscillating motion are discussed. The uniformly valid solution which is applicableto all kinds of cylinder wall cases at waterline point is obtained. It is pointed out that thesolution obtained by Holford[J] for the vertical oscillating motion of a cylinder is incomplete.The reason why his solution cannot go over to that for the case of vertical cylinder wall atwaterline point is also pointed out.

Phase-dependent properties for absorption and dispersion in a closed equispaced three-level ladder system

It is shown that in a closed equispaced three-level ladder system, by controlling the relative phase of two applied coherent fields, the conversion from absorption with inversion to lasing without inversion (LWI) can be realized; a large index of the refraction with zero absorption can be gotten; considerable increasing of the spectrum region and value of the LWI gain can be achieved. Our study also reveals that the incoherent pumping will produce a remarkable effect oil the phase-dependent properties of the system. Modifying value of the incoherent pumping can change the property of the system from absorption to amplification and enhance significantly LWI gain. If the incoherent pumping is absent, we cannot get any gain for any value of the relative phase. (c) 2007 Elsevier GmbH. All rights reserved.

Upper hybrid resonance absorption and scattering from a plasma column

The electromagnetic scattering and absorption properties of small (kr~1/2) inhomogeneous magnetoplasma columns are calculated via the full set of Maxwell's equations with tensor dielectric constitutive relation. The cold plasma model with collisional damping is used to describe the column. The equations are solved numerically, subject to boundary conditions appropriate to an infinite parallel strip line and to an incident plane wave. The results are similar for several density profiles and exhibit semiquantitative agreement with measurements in waveguide. The absorption is spatially limited, especially for small collision frequency, to a narrow hybrid resonant layer and is essentially zero when there is no hybrid layer in the column. The reflection is also enhanced when the hybrid layer is present, but the value of the reflection coefficient is strongly modified by the presence of the glass tube. The nature of the solutions and an extensive discussion of the conditions under which the cold collisional model should yield valid results is presented.

I. Electronic states of heavily-doped molecular crystals--naphthalene. I. Theoretical. II. Experimental. II. Lowest singlet and triplet excited states of pyrazine

PART I

The energy spectrum of heavily-doped molecular crystals was treated in the Green’s function formulation. The mixed crystal Green’s function was obtained by averaging over all possible impurity distributions. The resulting Green’s function, which takes the form of an infinite perturbation expansion, was further approximated by a closed form suitable for numerical calculations. The density-of-states functions and optical spectra for binary mixtures of normal naphthalene and deuterated naphthalene were calculated using the pure crystal density-of-state functions. The results showed that when the trap depth is large, two separate energy bands persist, but when the trap depth is small only a single band exists. Furthermore, in the former case it was found that the intensities of the outer Davydov bands are enhanced whereas the inner bands are weakened. Comparisons with previous theoretical calculations and experimental results are also made.

PART II

The energy states and optical spectra of heavily-doped mixed crystals are investigated. Studies are made for the following binary systems: (1) naphthalene-h₈ and d₈, (2) naphthalene--h₈ and αd₄, and (3) naphthalene--h₈ and βd₁, corresponding to strong, medium and weak perturbations. In addition to ordinary absorption spectra at 4˚K, band-to-band transitions at both 4˚K and 77˚K are also analyzed with emphasis on their relations to cooperative excitation and overall density-of-states functions for mixed crystals. It is found that the theoretical calculations presented in a previous paper agree generally with experiments except for cluster states observed in system (1) at lower guest concentrations. These features are discussed semi-quantitatively. As to the intermolecular interaction parameters, it is found that experimental results compare favorably with calculations based on experimental density-of-states functions but not with those based on octopole interactions or charge-transfer interactions. Previous experimental results of Sheka and the theoretical model of Broude and Rashba are also compared with present investigations.

PART III

The phosphorescence, fluorescence and absorption spectra of pyrazine-h₄ and d₄ have been obtained at 4˚K in a benzene matrix. For comparison, those of the isotopically mixed crystal pyrazine-h₄ in d₄ were also taken. All these spectra show extremely sharp and well-resolved lines and reveal detailed vibronic structure.

The analysis of the weak fluorescence spectrum resolves the long-disputed question of whether one or two transitions are involved in the near-ultraviolet absorption of pyrazine. The “mirror-image relationship” between absorption and emission shows that the lowest singlet state is an allowed transition, properly designated as ¹B_3u ← ¹A_1g. The forbidden component ¹B_2g, predicted by both “exciton” and MO theories to be below the allowed component, must lie higher. Its exact location still remains uncertain.

The phosphorescence spectrum when compared with the excitation phosphorescence spectra, indicates that the lowest triplet state is also symmetry allowed, showing a strong 0-0 band and a “mirror-image relationship” between absorption and emission. In accordance with previous work, the triplet state is designated as ³B_3u.

The vibronic structure of the phosphorescence spectrum is very complicated. Previous work on the analysis of this spectrum all concluded that a long progression of v_6a exists. Under the high resolution attainable in our work, the supposed v_6a progression proves to have a composite triplet structure, starting from the second member of the progression. Not only is the v_9a hydrogen-bending mode present as shown by the appearance of the C-D bending mode in the d₄ spectrum, but a band of 1207 cm^-1 in the pyrazine in benzene system and 1231 cm^-1 in the mixed crystal system is also observed. This band is assigned as 2v_6b and of a_1g symmetry. Its anonymously strong intensity in the phosphorescence spectrum is interpreted as due to the Fermi resonance with the 2v_6a and v_9a band.

To help resolve the present controversy over the crystal phosphorescence spectrum of pyrazine, detailed vibrational analyses of the emission spectra were made. The fluorescence spectrum has essentially the same vibronic structure as the phosphorescence spectrum.

Molecular Antennas and Photoactive Nanomaterials based on Energy Transfer Processes

110 p.

Yb^3＋掺杂锌锗碲酸盐玻璃的热分析、光谱和激光性质

设计了组成为0．70TeO2-(0．20-x)ZnO-xGeO2—0．05La2O3-0．025K2O-0．025Na2O-0．01Yb2O3(摩尔分数x=0,0．05，0．10，0．15和0．20)的碲酸盐激光玻璃，测试了热学性质、吸收光谱、荧光光谱和荧光寿命。计算了Yb^3+离子的吸收截面、受激发射截面、荧光有效线宽等参数。结果表明，组成为0．70TeO2-0．20GeO2-0．05La2O3-0．025K2O-0．025Na2O的玻璃具有优于著名的碲锌钠(TZN)玻璃的热稳定性，高的受激发射截面(1

Yb：铅锌镧碲酸盐玻璃的热学、光谱和激光性质

研究了摩尔组分为70TeO2-(20-x)ZnO-xPbO-5La2O3-2.5K2O-2．5Na2O(x=0，5，10，15，20)的新型多元铅锌镧碲酸盐激光玻璃，外掺Yb2O3为玻璃摩尔组分的1％，测试了试样的物理性质及吸收光谱、荧光光谱和荧光寿命，计算了Yb^3+的吸收截面、受激发射截面、荧光有效线宽等光谱参数，结果表明：该系列玻璃都具有良好的热学稳定性((Tx-Tg)>195℃，高于TZN玻璃(118℃))；当X=15时，样品具有较好的光谱性质：高的受激发射截面(1．25pm^2)、长的荧光寿命(

掺铒高硅氧玻璃光谱性质的研究

应用Judd-Oflet理论计算了新型掺铒高硅氧玻璃中铒离子的强度参量Ωt（t=2，4，6），Ω2=8．15×10^-20,Ω4=1．43×10^-20,Ω6=1．22×10^-20，相比于其他氧化物玻璃，表现出较大的Ω2,6值，反映了铒离子周围的近邻结构不对称性和Er-O键的离子键成分较高．利用McCumber理论计算得到了能级4I13/2→4I15/2跃迁的受激发射截面为σc=O．51pm^2．这种高硅氧玻璃掺铒离子浓度尽管高于石英光纤的掺杂浓度10倍左右，其荧光寿命和量子效率仍达到6．0ms和66．