The Vibrational Spectra of 9-Fluorenone and Some of Its Isotopic Isomers

Abstract

Vibrational spectra of 9-Fluorenone, 9-Fluorenone-¹⁸O and 9-Fluorenone-d₈ have been recorded in the solid state and solutions in the infrared and (4000–100 cm^?1) and in the Raman (4000–50 cm^?1). Differential infrared linear dichroic spectra have also been measured. The assignment of the vibrational bands is performed using the group vibrational concept, isotopic shifts and polarization features of the normal modes.     

Fluorescence and absorption spectra of 9, 10-diazaphenanthrene solutions at 77°K

The S₁(n, √^*) ? S₀ fluorescence and absorption spectra of 9, 10-diazaphenanthrene solutions in hydrocarbons possess at 77°K a quasilinear structure (Shpolskii effect). In the frozen n-hexane matrix (c = 10^-4 M) the fluorescence spectrum displays a triplet structure (22 181, 22 169 and 22 149 cm^-1 for the O-O transition). The spectra of 9, 10-diazaphenanthrene solution are shifted towards the red compared with those of the single crystal (～ 900 cm^-1). A good agreement between the calculated and experimental values of this shift is obtained. A strong concentration effect on the structure of the spectra is discussed. A quasilinear structure is observed also in the second absorption band.     

RCCo_3(CO)_9的电化学和RCCo_3(CO)_9~-的ESR谱研究

本文对三种RCCo_3(CO)_9及相应的自由基进行了电化学和ESR谱研究.电化学研究表明,RCCo_3(CO)_9被还原为自由基的难易与R的性质有关,RCCo_3(CO)_9在室温下可以稳定存在.在对分子轨道对称性分析的基础上对簇合物自由基的ESR谱进行了讨论.确定了超精细偶合常数的符号和未成对电子占据轨道的性质,计算了Co的3d轨道和4s轨道的自旋密度.     

小檗碱和9-O取代衍生物紫外光谱及构效研究

在水溶剂中,采用含时密度泛函理论(TD-DFT)和Multiwfn波函数分析软件中空穴-电子分析探究小檗碱及其衍生物紫外光谱电子激发特征,进而讨论构效关系。理论紫外光谱与实验光谱吻合较好,其中243 nm和416 nm处的两个吸收峰可认为是与小檗碱及其衍生物药性相关的特征吸收峰。小檗碱9-O处3-溴代丙基的取代不仅未引起吸收峰位置的变化,且提高O供电子能力,增强吸收峰强度;而2-氯代乙酰基、2-溴代乙酰基、环丙沙星的取代使9-O处氧对小檗碱母体无供电子能力,导致吸收峰红移。a、b环及9-O处氧是小檗碱及其衍生物激发过程中供电子体,c环是电子受体,尤其N处。有望对今后小檗碱衍生物合成设计提供一定的理论指导。     

Photoluminescence of manganese-doped LiNaGe4O9 crystals

The excitation spectra and photoluminescence spectra of manganese-doped LiNaGe₄O₉ crystals have been studied experimentally. It has been shown that the manganese ions provide strong red and weak yellow-green luminescences, whose intensities differently change upon the transition of the crystal from the paraelectric to ferroelectric phase. The possible localization and charge state of the manganese ions in LiNaGe₄O₉ crystals have been discussed.     

Stimulated-echo NMR spectroscopy of 9Be and 7Li in solids: method and application to ion conductors

The generation of pure quadrupolar stimulated-echo spectra is successfully demonstrated for the spin-3/2 probe 9Be in a single crystal of triglycine fluoberyllate. This solid exhibits a paraelectric-to-ferroelectric phase transition. From experiments carried out for various mixing times no indications for a slow soft mode could be detected in this crystal. Then ion conducting lithium metal phosphates were studied using 7Li, another spin-3/2 probe which allows for a non-selective excitation of the entire NMR spectrum. In the indium and the scandium phosphates ultra-slow Li hopping processes could be detected directly via the stimulated-echo technique in a time range of up to four orders of magnitude. Due to the relatively large gyromagnetic ratio and thus strong dipolar interactions of 7Li no pure quadrupolar echoes could be generated. However, from a variation of the evolution times the quadrupolar effects could be separated from the dipolar ones. Finally, the differences in the ion hopping times of lithium indium phosphate and of lithium scandium phosphate are briefly discussed.     

Mass spectrometric and ab initio study of the interaction between 9-methylguanine and amino acid amide group

The temperature dependent field ionization mass spectrometry method combined with ab initio calculations was used to determine the interaction energies and the structures of 9-methylguanine-acrylamide dimers. Acrylamide mimics the side chain amide group of the natural amino acids asparagine and glutamine. The experimental enthalpy of the dimer formation derived from the van't Hoff plot is ?59.5 ± 3.8 kJ mol^?1. The value is higher than interaction energies between acrylamide and other nucleic acid bases which were determined to be ?57.0 for 1-methylcytosine, ?52.0 for 9-methyladenine, and ?40.6 kJ mol^?1 for 1-methyl-uracil. In total, eight hydrogen bonded dimers formed by the three lowest energy 9-methylguanine tautomers and acrylamide were found in the quantum chemical calculations performed at the DFT/B3LYP/6-31++G?? and MP2/6-31++G?? levels of theory. The relative stability and the interaction energies of the dimers were calculated accounting for the basis set superposition error and the zero-point vibrational energy correction. The lowest energy dimer found in the calculations is formed by acrylamide (Ac) with the keto tautomer of 9-methylguanine (Gk). It is stabilized by two intermolecular H bonds, C6=O(Gk) · · · H—N(Ac) and Nl—H(Gk) · · ·O(Ac), and it is more stable than the second lowest energy dimer by ≈ 25 kJ mol^?1. The calculated interaction energies of the lowest energy 9-methylguanine-acrylamide dimer are ?65.0 kJ mol^?1 and ?67.7 kJ mol^?1 at the MP2 and DFT levels of theory, respectively. The experimental enthalpy of the dimer formation is in good agreement with both the calculated interaction energies of the GkAc dimer and much higher than the interaction energies calculated for all other 9-methylguanine-acrylamide dimers. This proved that only one dimer was present in the experimental samples. To verify whether acrylamide is a good model of the amino acid-amide group, we performed direct calculations of the 9-methylguanine-glutamine dimers at the same levels of theory as used for the complexes involving acrylamide. The interaction energies found for the lowest energy 9-methylguanine-glutamine dimer are ?65.1 kJ mon^?1 (MP2/6-31++G??) and ?66.2 kJ mol^?1 (DFT/B3LYP/6-31++G??) and these values are very close (within 0.5 kJ mol^?1) to the interaction energies obtained for the 9-methylguanine-acrylamide dimers.     

Two-center molecular states in9B,9Be,10Be,and10B

The molecular states in the mass 9 and 10 nuclei, which consist of two α-particles plus one or two valence nucleons (protons or neutrons) are discussed. Arguments for the existence of two-center dimers as excited states in¹⁰Be and corresponding resonances (p+⁹Be) in¹⁰B are given. The latter states are observed as anomalous (non statistical) population in the final state interactions in thep+⁹Be channel in various heavy ion collisions. With the establishment of two-center states (dimers) based on the αα-potential and a localized binding via two nucleons in¹⁰Be, the existence of more extended structures (multimers) by adding (α2n) structures to¹⁰Be* is postulated. Generally clustering intoα-particles and nucleons in terms of molecular states is expected to occur at excitation energies close to the threshold for these substructures in analogy to the clustering rules of Ikeda forα-particle nuclei. Consequences to clustering properties of neutron rich nuclei are discussed.     

Eu3+激活的La2Mo2O9红色荧光粉的制备与性能

利用高温固相法制备了Eu³⁺掺杂的La₂Mo₂O₉红色荧光粉,并对这种荧光粉的结构及发光性质进行了研究。XRD结果表明,实验合成了单一立方相的La₂Mo₂O₉荧光粉体。该荧光粉的激发光谱由一宽带和一系列的锐峰组成;发射光谱由一系列锐峰组成,这些都与Eu³⁺的特征跃迁⁵D_J(J=0,1)和⁷F_J(J=1~4)相对应。结果表明该荧光粉可被395nm的紫外光和470nm的可见光有效激发,并发出峰值位于620nm左右的红光,亮度可达到传统红色荧光粉Y₂O₂S:Eu³⁺的1.5倍以上,这表明它可以作为蓝+黄模式白光LED的红色补光粉,也可以作为UV-LED激发三基色荧光粉体系中的红色荧光粉。研究了Eu³⁺的掺杂浓度以及不同助熔剂对样品发光性质的影响。Eu³⁺的摩尔分数为0.3时,发光强度达到最强。质量分数为3%的NH₄Cl作为助熔剂时效果最好。     

一种9-苯基芴位阻功能化的苯胺中间体的设计合成、表征及其光电性质

以醋酸为溶剂、浓硫酸为催化剂在120 ℃回流24 h, 通过傅克反应设计合成了一种大体积位阻型9,9-二芳基芴中间体[9-(4-苯胺基)-9-苯基芴](FPPhNH₂)。通过核磁氢谱、质谱、红外等方法对该化合物的分子结构进行了详细表征。核磁氢谱和红外光谱分别在6.55 ppm,3 481和3 385 cm-1显示该化合物的特征官能团-氨基。用紫外-可见光谱和荧光光谱对9-(4-苯胺基)-9-苯基芴的光学性质进行了表征和初步探讨。研究结果表明, 具有大体积空间位阻效应的9-(4-苯胺基)-9-苯基芴在二氯甲烷溶液中有四个主要吸收峰, 其吸收波长分别为243,257,298和311 nm; 在波长为308 nm的谱激发下,得到发射波长为300～500 nm的发射光谱曲线, 其荧光光谱最大发射波长为328 nm, 且在405 nm左右有一个细小的峰并有一个长的拖尾至500 nm, 这可能源于苯胺基团中分子间氢键所引起的。恰当的荧光发射范围(300～500 nm), 使其能够和经典蓝光客体材料双(4,6-二氟基吡啶-N,C2)吡啶甲酰合铱(FIrpic)的吸收光谱有较大的重叠(300～500 nm)。通过巧妙的分子裁剪, 或可得性能优异的主体材料, 进而使制备高性能的发光器件成为可能。为了进一步了解该化合物的光电性能, 以乙腈为溶剂, 以四丁基六氟磷酸胺为电解质, 通过循环伏安法对该化合物的电化学性能进行了表征。其起始氧化电位和还原电位分别为0.898和-0.759 V, HOMO和LUMO能级分别为-5.38和-3.72 eV, 其较高的HOMO能级和较低的LUMO能级有利于空穴和电子的注入/传输, 这将进一步优化成性能优异的主体材料, 并为进一步制备性能优异的有机半导体发光器件提供有益参考。     

Gain and excited singlet and triplet state absorption spectra of some 9-acetoxy-10(halogenoacetoxy)phenylanthracenes

An apparatus for, optical gain spectra measurements is described, which has been used to determine the gain spectra of several halogen substituted derivatives of 9-acetoxy-10(2-acetoxy)phenylanthracenes. Using the determinedS ₁- andT ₁-excited state absorption spectra and other spectroscopic data the gain spectrum have been computed. The changes of the determined laser parameters and spectroscopic data of the halogen substituted derivatives are discussed with reference to the intramolecular heavy atom effect.Work partially supported within the project CPBP01.06 and from the Foreign Commission at the University of Bremen     

Atom-solid 3p level binding energy shift of transition metals Cr,Mn, Fe,Co, and Ni

Binding energy shifts between atomic and solid phases for transition metals Cr, Mn, Fe, Co, and Ni have been obtained for 3p subshells from simultaneously recorded atomic vapor and solid state spectra. This experimental technique provides higher accuracy in comparison to separate measurements and allows direct determination of the shifts. The observed shift values are compared to values obtained using the semiempirical Born–Haber cycle method and the peak structures of the solid state photoelectron spectra are compared to atomic 3p spectra. The binding energy shift of Cr is found to be much smaller than that of the other studied elements.     

N-Triazinyl Derivatives of 1- and 9-aminoanthracene: Synthesis and Photo-Physical Properties

New N-triazinyl derivatives were synthesized by reaction of cyanuric chloride with 1- and 9-aminoanthracenes and subsequent nucleophilic substitution of chlorine atoms on triazinyl ring with methoxy and/or phenylamino groups. The compounds were characterized by ¹H and ¹³C NMR and mass spectra. The influence of the chemical structure and solvent polarity on the UV/Vis absorption and fluorescence spectra and fluorescence quantum yields were investigated. Semi-empirical computations revealed highly polar CT states in singlet excited state manifold connected with charge-transfer from the hydrocarbon moiety to the triazinyl ring. The relationships between the CT-to-emitting state energy gap, solvent polarity and fluorescence quantum yield were discussed.     

Molar coefficients of extinction for IR absorption bands of Ni(II) acetylacetonate, ketoiminate, and trifluoroacetylacetonate

We have studied IR absorption spectra (within the spectral range of 4000-200 cm⁻¹ of the intracomplex chelate compounds Ni(II) bis-acetylacetonate, Ni(II) bis-ketoiminate, and Ni(II) bis-trifluoroacetylacetonate and have given a full interpretation and comparison of the spectra of these compounds in dissolved and solid states. The reasons for the differences in the spectra are discussed. The molar coefficients of extinction for the absorption bands are calculated. Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3, Akad. Lavrent’ev Ave., Novosibirsk, 630090, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 5, pp. 775–780, September–October, 1998.     

Self-trapping of excitons and lattice defect production in solid rare gases

A comparison of the calculated fluorescence spectra of solid and liquid rare gases with the experimental data makes it probable that in solid rare gases the exciton self-trapping is accompanied by defect production, here the defect production being the fundamental mechanism of the relaxation of exciton to its ground state. The comparison of the fluorescence spectra of solid and liquid phases makes it possible to forecast the production of radiation damages. A conjectural relationship between exciton cavities and nucleation processes proceeding in bubble chambers are briefly discussed.Dedicated to Professor Miroslav Trlifaj on the occasion of his sixtieth birthday.     

Analysis of spectra of acoustic signals generated by high-power pulsed laser radiation propagating in the atmosphere. I. Spectra of local plasma formations

Results of theoretical and experimental investigations into the spectra of acoustic signals generated by high-power pulsed laser radiation propagating in the atmosphere in the breakdown mode are given in the present paper. In Part I, results of theoretical and experimental investigations into the spectra of acoustic signals from laser breakdown initiated on a single solid aerosol particle and an ensemble of monodisperse particles depending on the particle material and sizes are presented. In Part II, spectra of acoustic signals from laser sparks in the atmosphere are analyzed, and the special features of the spectra of acoustic signals from individual plasma formations and discrete laser sparks are discussed. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 74–80, November, 2005.     

Interpretation of the vibrational spectra of polycrystalline adenine

The infrared and Raman spectra of the tetramer of the adenine N₉H are calculated and analyzed. The vibrational spectra of polycrystalline adenine are interpreted. It is demonstrated that the method for calculating the vibrational spectra of molecular complexes formed by hydrogen bonds can be used for interpreting the vibrational spectra of polyatomic molecules in the solid state.     

Raman and IR spectra of the cation‐deficient Aurivillius layered crystal Bi2W2O9

Raman and IR spectra of Bi₂W₂O₉, the m = 2 member of the cation‐deficient Aurivillius phase, have been measured. The obtained spectra are discussed using the factor group approach for the orthorhombic Pna2₁(C_2v⁹) space group. The results are compared with those obtained for Bi₂WO₆ and some m = 2 members of Aurivillius family of bismuth layered ferroelectrics. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational spectra and rotational isomerism of tripropargyl amine

The infrared spectra of tripropargyl amine were recorded from 250 to 4000 cm⁻¹ in the vapor, liquid and solid phases. The Raman spectrum of the liquid at room temperature was photoelectrically recorded and qualitative depolarization measurements were made. A comparative study of the infrared spectra in the fluid phase and in various solvents with that in solid phase reveals the existence of rotational isomers in the liquid and vapor phases. Various possibilities for rotational isomers with different point group symmetries are discussed.