Absorption and emission properties of the six isomeric di-pyridyl-ketones

The absorption and emission spectra of the six isomeric di-pyridyl-ketones have been investigated in solvents of different polarity. The experimental data have shown that the lowest singlet and triplet states of these molecules are due to nπ* excitation, localized on the carbonyl. CNDO/S calculations of singlet excitation energies on geometries optimized by means of MNDO were performed and found to be in satisfactory agreement with the experimental data.     

Stability of transition metal complexes involving three isomeric quinolyl hydrazones

The stability constants of three isomeric quinolyl hydrazones; {4,6-(para); 4,7-(meta) and 4,8-MeBHQ(ortho)} towards some bivalent metal ions have been determined in 75% solvent (dioxane, isopropanol, ethanol and methanol)-water by a pH-titrimetry. The insertion of the Me-group in the 8-position decreases the stability of the complexes to a great extent. The complexation of the ortho-derivative is endothermic, whereas that of the para-derivative is exothermic. Using the solvent parameters, the stability constants of the para-derivative towards Co(II), Ni(II) and Cu(II) ions were evaluated in aqueous medium by five different methods. Also, the electronic absorption spectra of the ortho-hydrazone have been studied in solvents of various polarities to investigate the dependence of the band shift (Δ?) on the solvent parameters viz. 1/D, Z, E(T), DN, AN and (α, β, π*). The interaction of the hydrazones with CoCl(2)·6H(2)O afforded an octahedral complex in case of the ortho-hydrazone and square planar complexes in case of the meta- and para-hydrazones.     

Synthesis and structural analysis of isomeric pyridinophanes and thiacyclophanes

A one-pot synthesis of structurally isomeric tetrathiacyclophanes through four-centre coupling reactions of suitable bromides and thiols is reported. The structures of the isomers were confirmed by spectroscopy and XRD analysis. Single crystal X-ray analysis reveals interestingly shaped molecular structures with large cavities.     

Ferrocene derivatives,Part 69 Preparative separation of isomeric trisubstituted ferrocenes

Summary Mixtures of positional isomers of trisubstituted ferrocenes can conveniently be separated on a preparative scale by applying medium-pressure liquid chromatography to suitable intermediates. By this technique formyl, hydroxymethyl, and dimethylaminomethyl 1,2-dimethyl-and 1,2-tetramethylene ferrocene, resp., (2, 3, 4 and6, 7, 8, resp.) were prepared as pure isomers (on a gramscale) by appropriate interconversion and chromatographic separation steps.

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Präparative Isomerentrennung von trisubstituierten Ferrocenen. 69. Mitt. über Ferrocenderivate

Zusammenfassung Mischungen von stellungsisomeren, trisubstituierten Ferrocenen können auch im präparativen Maßstab unter Anwendung der Mitteldruckchromatographie auf geeignete Zwischenprodukte glatt getrennt werden. Mit Hilfe dieser Technik wurden Formyl-, Hydroxymethyl- und Dimethylaminomethyl-1,2-dimethyl- bzw. 1,2-tetramethylen-ferrocen (2, 3, 4 bzw.6, 7, 8) durch Anwendung geeigneter Umwandlungs- und Chromatographie-Schritte im Grammaßstab isomerenrein erhalten.

     

Thermodynamic study of 2-methyl-tetrahydrofuran with isomeric chlorobutanes

Excess molar volumes, V^E, isentropic compressibility deviations, Δκ_S, and excess molar enthalpies, H^E, for the binary mixtures 2-methyl-tetrahydrofuran with 1-chlorobutane, 2-chlorobutane, 2-methyl-1-chloropropane and 2-methyl-2-chloropropane have been determined at temperatures 298.15 and 313.15 K, excess molar enthalpies were only measured at 298.15 K. We have applied the Prigogine-Flory-Patterson (PFP) theory to these mixtures at 298.15 K.     

Study of the molecular configuration and the dipole moment in fluorinated liquid crystals

We have investigated the relationship between the molecular configuration and dipole moment of some fluorinated liquid crystals (LCs). The geometries of the molecules were preliminarily optimized at empirical AM1 and then were further optimized at B3LYP/6‐31G(d) level. The dipole moment has been calculated. It is strongly influenced by the position and number of fluorine substituents in the benzene ring of the molecule. The polarizability, mean polarizabilities, and anisotropic polarizability of the phenylbicyclohexane (PBC) fluorine substituents are also given and discussed. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Differentiation of isomeric allylic alkenyl methyl ethers by Raman spectroscopy

The Raman spectra of several pairs of alkenyl methyl ethers of general structure R¹R²CCR⁵C(R³R⁴)OCH₃ and R¹R²C(OCH₃)C(R⁵)CR³R⁴ (R¹, R², R³, R⁴, R⁵ = H or C_nH_2n+1, n = 1-3) are reported and discussed, with a view to establishing whether Raman spectroscopy offers a viable means of distinguishing between these isomeric unsaturated species. Key bands associated with the ν(sp₂CH) and ν(CC) stretching modes are found to be particularly useful in this connection: R¹R²CCHCH₂OCH₃ and R¹R²C(OCH₃)CHCH₂ ethers (R¹, R² = CH₃, C₂H₅) are easily distinguished on this basis. Differentiation of their lower homologues, R¹CHCHCH₂OCH₃ and R¹CH(OCH₃)CHCH₂ (R¹ = CH₃, C₂H₅, C₃H₇), by similar means is also quite straightforward, even in cases where cis and trans isomers are possible. Pairs of isomeric ethers, such as CH₃CHC(CH₃)CH₂OCH₃ and CH₃CH(OCH₃)C(CH₃)CH₂, in which the structural differences are more subtle, may also be distinguished with care. Deductions based on bands ascribed to the stretching vibrations are usually confirmed by consideration of the signals associated with the corresponding δ(sp₂CH) deformation vibrations. Even C₂H₅CHCHCH(C₃H₇)OCH₃ and C₃H₇CHCHCH(C₂H₅)OCH₃ are found to have distinctive Raman spectra, but differentiation of these closely related isomers requires additional consideration of the low wavenumber region.     

Relaxation behavior,intramolecular interactions,and local motions on monosubstituted esters of poly(itaconic acid)

The mechanical relaxation spectrum of poly(monocyclohexylmethylene itaconate) (PMCMI) exhibits two well-developed absorptions in the glassy state that in increasing temperature order are named γ and β absorptions. Owing to the restricted conformational versatility of the backbone, the polymer presents a weak glass-rubber relaxation whose intensity is significantly lower than that of the γ absorption. Comparison of the mechanical spectrum of this polymer with that of poly(dicyclohexylmethylene itaconate) (PDCMI) allows the conclusion that the β relaxation is produced by motions in which the ? COOCH₂C₆H₁₁ side groups are involved. The location of the mechanical γ peak suggests that this absorption is produced by flipping conformational transitions in the cyclohexyl residue. Three dielectric absorptions are observed in the glassy state of PMCMI which in increasing temperature order are called δ, γ, and β relaxations. Both the location and the activation energy of the dielectric and mechanical β absorptions suggest that both relaxations are caused by the same molecular motions. Dipolar interactions in the liquid and glassy state are calculated and the results compared with those experimentally evaluated. © 1994 John Wiley & Sons, Inc.     

吡啶基团的对称性和离子化对分子双光子吸收截面的影响

采用超快速激光光谱方法研究了含吡啶基团的四个联苯乙烯衍生物及两个杂环分子(A: 4,4’-二(2-(4-吡啶基)乙烯)联苯; B: 4,4’-二(2-(2-吡啶基)乙烯)联苯; C: 1-甲基-4-(2-(4’-(2-(4-吡啶基)乙烯基)-4-联苯)乙烯基)吡啶碘盐; D: 1-甲基-2-(2-(4’-(2-(2-吡啶基)乙烯基)-4-联苯)乙烯基)吡啶碘盐; E: 4-(2-(9-丁基-9氢-3-咔唑)乙烯基)-1-甲基吡啶碘盐; F: 4-(2-(9-丁基-9氢-3-咔唑)乙烯基)-1-甲基喹啉碘盐)的结构-性能关系. 实验结果显示双光子吸收截面最大的是分子E, 高达617.3 GM; 最小的是分子B, 为19.3 GM(1 GM=10^-50 cm⁴·s·photon^-1). 实验研究结果表明, 分子中吡啶基团的对称性及其离子化对分子双光子吸收截面起很重要的作用; 进一步用理论计算证实了以上实验结论并对其机制进行了分析讨论.     

Dipole moments and structure of poly(epoxypropylcarbazole)

The mean-square molecular dipole moments 〈μ²〉 of carbazole, N-ethylcarbazole and of the sequence of poly(epoxypropylcarbazole) (PEPCa) oligomers of various molecular weights have been evaluated in solutions of these organic compounds in dioxan. For PEPCa the values of 〈μ²〉 have also been determined in the solid state. On the basis of the experimental results and of molecular mechanics calculations it has been shown that the orientation of the lateral group of PEPCa favors noninteracting racemic dyads. The temperature-dependence of the effective dipole moment of solid PEPCa follows the Onsager theory above 295 K.     

Absorption and emission spectra of the lowest triplet state in hexachloroacetone

T₁ ← S₀ absorption and T₁ → S₀ phosphorescence spectra of neat cystalline hexachloroacetone have been analyzed at 4.2°K. From the lifetime and energy the upper state is assigned as ³nπ^*. The spectra are sharp compared to other aliphatic ketones, with the 0-0 band at 26 248 ± 2 cm ^?1. The phosphorescence shows two strong progressions; one involving the CO stretching mode at 1784 cm^?1 (x), the other a long progression of at least 8 bands involving a mode at 143 cm^t-1 (a). The 143 cm^?1 progression forming mode can best be asigned to the CO out-of-plane wagging vibration. The absorption shows the same two strong progressions, reduced in frequency to 1270 cm^t-1 and 123 cm^?1, respectively, but with the progression in mode a broadened with increasing n. The broadening is interpreted as arising from inversion doublets; the close harmonicity up to n = 5 allowing the potential barrier to inversion to be estimated as > 700 cm^?1. A feature of the spectra is the absence of low frequency torsional modes suggesting lack of pseudo Jahn-Teller distortion of the triplet state potential surface. For comparison, the phosphorescence of crystalline hexafluoroacetone was also studied at 4.2°K. The spectrum exhibits broad bandedness with a 00 band tentatively assigned at 26 870 ± 20 cm^?1.     

Absorption and emission spectra of Ce3+ in elpasolite lattices

The experimental determination of the electronic energy levels for Ce(3+) in some chloroelpasolite hosts for both the ground 4f(1) and the excited 5d(1) configurations is described. High-resolution f-f absorption and f-(2)T(2g) d absorption and emission spectra have been recorded at low temperatures for Ce(3+) diluted into various hexachloroelpasolite lattices. A fluorescence spectrum at approximately 50 000 cm(-1) is tentatively assigned to the emission from the highest 5d crystal field level, (2)E(g), of a Ce(3+) impurity in Cs(2)NaErCl(6), enabling the values of all the energy levels of both the 4f(1) and 5d(1) configurations to be given for Ce(3+) in elpasolite hosts. Vibronic structure superimposed on the electronic transitions is analyzed in terms of a simple configurational coordinate model involving the ground and excited configurations. It is found that the difference in the Ce-Cl bond length between the 4f(1) and 5d(1) configurations is approximately 0.04 A. Ab initio model potential calculations on the (CeCl(6))(3-) cluster embedded in a reliable representation of the Cs(2)NaYCl(6) host support these conclusions.     

Absorption spectra,emission spectra,and magnetic susceptibility of chromium in sodium-β-alumina

Absorption spectra, emission spectra, and magnetic susceptibility from 4.2 to 300°K have been measured for β-alumina doped with $\text{2w}\text{o}$ chromium. Chromium-doped β-alumina sintered in air was found to contain only Cr(IV) even though Cr(III) was the oxidation state initially present. Heating air-sintered samples at 1200°C in $\text{10\% H}{}_2\text{90\% N}{}_2$ for 5 hr reduced the Cr(IV) to Cr(III). The absorption spectra for Cr(IV) and Cr(III) have been fitted to the Tanabe-Sugano diagram and Dq and B were calculated. Results are consistent with the assignment of both Cr(III) and Cr(IV) to octahedral coordination sites in β-alumina. A parallel study of chromium doped α-alumina also showed the existence of Cr(IV) and Cr(III) in that host lattice depending on the firing atmosphere.     

Solvent Effects on the Absorption and Emission Spectra of Some Nematic Liquid Crystals: Determination of Dipole Moment and First-Order Hyperpolarizability

The effect of solvent on the absorption and fluorescence spectra of two liquidcrystalline molecules LC1 and LC2 were studied. These data were used to evaluatethe values of the change in the dipole moment between the ground and excitedstate and the first-order hyperpolarizability in each solvent. The values of gives an indication of how these liquid crystalline samples can find applicationsas nonlinear materials. The values are in the range 1–1.9 × 10²⁹ esu for LC1and LC2. The values of indicate that these compounds can be used as goodnonlinear materials. Here solvatochromism has been used as an effective tool toestimate the hyperpolarizability in solution.     

Unique photochromism of two solid-emissive boron difluoride-based diarylethenes with isomeric structures

Two solid-emissive boron difluoride-based diarylethenes with isomeric structures are synthesized and the boron-difluoride chromophores are one part of the photoisomerization units in both diarylethenes. These two diarylethenes show similar fluorescent properties in the solid state as in dilute chloroform solutions because intermolecular planar π-π interactions are significantly alleviated as verified by their X-ray single crystal structures. However, only one of these two diarylethenes exhibits typical reversible absorption and fluorescence changes upon UV or visible light irradiation, and their diverse response to light irradiation is investigated by X-ray single crystal analysis and also DFT calculation. The investigation presented here provides valuable insight into the designing and development of diarylethene-based fluorescent switches in the solid state.     

Atmospheric-pressure ionization studies and field dependence of ion mobilities of isomeric hydrocarbons using a miniature differential mobility spectrometer

The ionization pathways and ion mobility were determined for sets of structural isomeric and stereoisomeric non-polar hydrocarbons (saturated and unsaturated cyclic hydrocarbons and aromatic hydrocarbons) using a novel miniature differential mobility spectrometer with atmospheric-pressure photoionization (APPI) to assess how structural and stereochemical differences influence ion formation and ion mobility. The analytical results obtained using the differential mobility spectrometry (DMS) were compared with the reduced mobility values measured using conventional time-of-flight ion mobility spectrometry (IMS) with the same ionization technique.The majority of differences in DMS ion mobility spectra observed among isomeric cyclic hydrocarbons can be explained by the formation of different product ions. Comparable differences in ion formation were also observed using conventional IMS and by investigations using the coupling of ion mobility spectrometry with mass spectrometry (APPI-IMS-MS) and APPI-MS. Using DMS, isomeric aromatic hydrocarbons can in the majority of cases be distinguished by the different behavior of product ions in the strong asymmetric radio frequency (rf) electric field of the drift channel. The different peak position of product ions depending on the electric field amplitude permits the differentiation between most of the investigated isomeric aromatics with a different constitution; this stands in contrast to conventional IMS in which comparable reduced mobility values were detected for the isomeric aromatic compounds.     

Microcolumn liquid chromatography of polycyclic aromatic hydrocarbons and some isomeric compounds on cyclodextrin stationary phases

Preparative-grade bonded β- and γ-cyclodextrin stationary phases were used as the packing material of liquid chromato-graphic analytical microcolumns. Although the resulting columns are characterized by relatively low efficiency, the high selectivity of the cyclodextrin phases nevertheless allows their successful use for the separation of different classes of isomeric compounds that are difficult to resolve on conventional LC stationary phases. Examples of baseline (or almost baseline) separations of a number of isomeric compounds, including isomeric polycyclic aromatic hydrocarbons, are presented to demonstrate the analytical potential of such columns. Retention behavior of the separated isomers is discussed based on the structure of the solute molecule and the possibility of its inclusion into the molecular cavity of cyclodextrin stationary phases.     

Dispersed Fluorescence Spectroscopy and Transition Dipole Moment of HCO β 2A′-X̄2A′

Dispersed fluorescence spectra of β ²A′ - x? ²A′ transitions are measured on exciting HCO to the vibrational levels (0,0,0), (0,0,1), (0,1,0) and (1,0,0) of β ²A′ in a gas cell. Vibrational energies of bound and resonant states are determined for energy up to 17 500 cm^?1 from the ground vibrational level of the x? ²A′ state. Rotationally resolved spectra of the bands β ²A′ - x? ²A′ 2⁰₃3⁰₁, 2¹₄ and 2⁰₂3¹₂ were recorded and analyzed. Abnormal intensities in the P, Q and R branches are due to the mechanism of “axis switching”. From the ratios of emission intensity of a- and b-type transitions, without taking into account the varied lifetimes of rotational states of the upper electronic state, the directions of transition dipole moments of these bands are determined to be 39 ? 43° to the inertial a axis.     

Ionization constants and fluorescence excitation and emission spectra of the isomeric benzo[a]pyrene phenols

The acid dissociation constants, for the ground and lowest excited singlet states of the benzo[a]pyrene phenols, are reported, and correlated with current thought on carcinogen activation. The corrected fluorescence excitation and emission spectra of these compounds and their anions are recorded. The shifts caused by ring hydroxylation of the parent compound, and the relative spectral band intensities for each phenol are compared to those of pyrene, in a brief assessment of spectral transition polarization in the phenols.