醇类溶剂溶剂化显色极性的理论分析

对一系列醇类溶剂分子进行了理论计算,运用多元线性回归分析方法从分子间相互作用的角度对四种溶剂化显色极性参数(E~T^N,π^*,Py和SPP)进行了理论分析。结果表明,对醇类溶剂而言,参数E~T^N和SPP实质上主要反映的是溶剂的氢键酸性性质;参数π^*中虽然包含了溶剂的极性因素,但同时与溶质-溶剂分子间的电荷转移相互作用有着密切的关系;而参数Py则较好地反映了溶剂的极性性质。     

7-吡啶吲哚同分异体结构与电子光谱性质的理论研究

运用密度泛函理论对7-吡啶吲哚可能存在的构型进行优化,计算异构体的几何构型、电子结构、前线分子轨道;应用含时密度泛函理论计算了异构体b,c和e的电子光谱性质以及溶剂效应对光谱性质的影响.结果表明,溶剂极性的增加使b的电子光谱蓝移,而c和e的电子光谱红移,且溶剂极性对最大吸收波长影响幅度较小.前线分子轨道分析,表明该类化合物的主要吸收光谱主要对应于分子中的HOMO→LUMO电子跃迁,且为π→π*跃迁.     

含氮配体过渡金属络正离子与[Ni(cdc)2]2-加合物的电子光谱和电导率研究

研究了10个含氮配体的过渡金属络正离子与[Ni(cdc)2]2-加合物在溶液和固体状态下的电子光谱和溶液电导率,发现电导率(Ω-1·cm2·mol-1)和加合物在Ha介质中π-π*跃迁带vmax(cm-1)值呈一致的变化关系.对吸收峰作出了归属,指定了负离子的MLCT带,并指出极性溶剂使MLCT带蓝移,π-π*跃迁带红移.     

洛汾碱衍生物的电子结构及光谱性质的理论研究

采用密度泛函理论(DFT)的B3LYP/6-31G*方法,对4种洛汾碱类化合物的几何构型进行了优化,在此基础上计算分子的电子结构,并结合有限场FF方法研究了二阶非线性光学(NLO)性质.用含时密度泛函理论(TD-DFT)对上述化合物分子进行吸收光谱的研究.研究表明在4,5-二-苯基-2-对甲酰苯基咪唑生色团中4,5苯环上引入硝基和3位N原子引入苄基改变分子的共轭平面,使二阶非线性极化率总有效值(βtot)减小,吸收峰总体蓝移.同时还发现,在CH2Cl2溶剂中a和c分子的λmax主要来源于HOMO→LUMO的π一π*跃迁,b和d分子的λmax主要来源于HOMO→LUMO+2的π→π*跃迁.     

双取代咔唑化合物的合成及光谱性质研究

以咔唑为分子主体,选择了3种不同的共轭小分子修饰到咔唑分子上,合成了3种A-π-D-π-A型ICT化合物,研究了其光谱性能、考察了不同极性溶剂对光谱的影响,及可能的ICT过程.结果表明化合物a具有优良的电荷转移效果,有望应用于微环境极性探针及有机光电材料领域.     

2,6-二(2-羟基苯乙烯基)-4-甲基均三嗪的合成与性质研究

设计合成了以三嗪基团为骨架的化合物2,6-二(2-羟基苯乙烯基)-4-甲基均三嗪(M1),利用核磁共振H谱和C谱对其结构进行了表征;并对目标化合物在甲醇和乙醚中的紫外,荧光光谱进行了研究.利用量子化学密度泛函理论的B3LYP方法,在6-311+G*水平上,对标题化合物分子构型进行了理论计算.通过实验发现随着溶剂极性增加,紫外吸收峰和荧光光谱的发射峰都发生红移,同时得到的计算光谱数值与实验值吻合较好.     

4-氨基-1,8-萘二酰亚胺的结构及光谱性质的理论研究

采用HF和密度泛函理论中的B3LYP和PBE0方法,在7个不同的基组下优化得到了4-氨基-1,8-萘二酰亚胺(ANI)的基态几何构型,用CIS/6-31+G(d)方法得到第一激发态几何构型,频率分析无虚频.在此基础上运用HF-CIS,TD-B3LYP和TD-PBE0方法研究了在气相及DMSO,DMF,MeCN,THF,CHCl3和EtOH溶剂中ANI的前线轨道及电子光谱.结果表明,HOMO→LUMO的跃迁是π→π*跃迁.随溶剂极性的增加,其最大吸收和荧光波长红移.用TD-B3LYP/6-31+G(d)方法得到的溶剂中ANI的吸收光谱计算值与实验值吻合性较好,但荧光光谱计算值与实验值有较大差异.进一步经线性拟合校正,ANI在非质子溶剂中的计算值与实验值能较好地吻合.计算显示激发态ANI具有较大的偶极矩,与解释相关荧光分子探针的光诱导电子转移方向选择性现象的光生电场理论一致.     

3,6-二(蒽醌-2-乙烯基)-N-乙基咔唑的合成及光谱性质研究

利用N-乙基咔唑和2-甲基蒽醌合成了一种A-π-D-π-A分子内电荷转移型化合物3,6-二(蒽醌-2-乙烯基)-N-乙基咔唑,并对该化合物的光化学和光物理行为进行了研究。荧光光谱表明,该化合物的发光行为对溶剂的极性非常敏感,随着溶剂极性的增大,其荧光最大发射峰有明显红移,并在强极性溶剂乙腈中出现了双荧光现象。该化合物的激发态和基态的偶极矩差值△μ为3.014D,发生了从给体(咔唑基)的N原子到分子两端受体(蒽醌)的羰基的分子内电荷转移。     

香豆素衍生物溶液的光谱和光物理行为

通过对一系列不同取代的香豆素化合物在不同溶剂中的光谱测定,研究了结构和溶剂极性对它们光物理行为的影响.发现了它们的光物理特征与其结构和多种溶剂极性参数间存在的一些关系,为进一步更好的利用这类化合物提供了重要依据.     

3-吡咯烷基苯并蒽酮的电子结构和光谱性质

苯并蒽酮衍生物在新型荧光材料、非线性光学材料和液晶显示材料等领域有较大的应用前景.本文采用量子化学方法优化了3-吡咯烷基苯并蒽酮的基态几何结构和第一单重激发态的几何结构,并与X射线晶体衍射实验值进行了对比.利用含时密度泛函理论(TD-DFT)的不同泛函,计算了3-吡咯烷基苯并蒽酮在气相和溶剂中的吸收和发射光谱,考察了它的电子结构和光谱特征,并分析了不同泛函、基组以及溶剂效应对吸收和发射光谱的影响.计算结果表明:3-吡咯烷基苯并蒽酮的最强吸收和发射光谱都是具有π→π*跃迁特征的电荷转移(CT)态;泛函B3LYP能较好地重现实验吸收能;而对于具有分子内电荷转移特征的激发态,泛函MPWK能较好地重现实验发射能.溶剂效应的计算表明,不同极性的溶剂对3-吡咯烷基苯并蒽酮的吸收光谱和发射光谱的影响较小.理论预测的光谱与实验结果一致.     

Absorption Spectra and Photoreactivity of Para-aminobenzophenone by Time-dependent Density Functional Theory

The absorption spectral properties of para-aminobenzophenone (p-ABP) were investigated in gas phase and in solution by time-dependent density functional theory. Calculations suggest that the singlet states vary greatly with the solvent polarities. In various polar solvents, including acetonitrile, methanol, ethanol, dimethyl sulfoxide, and dimethyl formamide, the excited S1 states with charge transfer character result from π→π* transitions. However, in nonpolar solvents, cyclohexane, and benzene, the S1 states are the result of n→π* transitions related to local excitation in the carbonyl group. The excited T1 states were calculated to have ππ* character in various solvents. From the variation of the calculated excited states, the band due to π→π* transition undergoes a redshift with an increase in solvent polarity, while the band due to n→π* transition undergoes a blueshift with an increase in solvent polarity. In addition, the triplet yields and the photoreactivities of p-ABP in various solvents are discussed.     

The effect of solvents on the electronic absorption spectra of mesoionic 1,8,4 thiadiazolium-2-thiolate derivatives

The electronic absorption spectra of 4,5-diphenyl-, 4-pheriyl-5-(4-fluorophenyl)-, 4-phenyl-5-(4-chlorophenyI)-, and 4-phenyl-.5-methyl-1,3,4-lhiadiazolium-2-thiolates have been measured in twenty-one pure solvents, aqueous ethanol and acetone solutions and cyclohexane-chloroform mixtures. They were found to exhibit three characteristic absorption bands; the first in the range 330-440 nm, the second at 260-280 run and the third near 200 ran. The first band was assigned to n → π* transition whereas the other two bands were assigned to π →π* transition. The n → π* transition band was found to be very sensitive, and the polarity of solvents, and some correlations between well-known solvent polarity parameters and the transition energies of these compounds have been presented.     

SPECTROSCOPIC STUDIES OF PURINES—I. FACTORS AFFECTING THE FIRST EXCITED LEVELS OF PURINE*

Abstract— Studies of purine absorption and emission in seven solvents differing greatly in dielectric constant and hydrogen bonding potential, reveal a variety of solvent effects. For example, the resolution of structure in the absorption spectrum, the position and/or intensity of the X₂ absorption band, the intensity of fluorescence, the magnitude of the long wave-lenth tail, and the position of the X₁ absorption band are differentially affected—in the order listed—by the solvents tested. Even though it is possible to correlate the extent of decrease in the n-π* tail with increasing solvent dielectric constant, probably alterations in all of these spectroscopic parameters depend most critically upon the ability of the various solvents to form hydrogen bonds with the hydrogen on N9 and/for with the non-bonding electrons on the purine nitrogens: it is tentatively concluded that the probability of hydrogen bonding is directly correlated with the electronegativity of the aza nitrogens (N7 > N3 > N1). In solvents like isopropanol not all of the non-bonding electrons must be solvated maximally in most purine molecules since there is appreciable fluorescence under conditions where a long wavelength tail is readily observed in the absorption spectrum (alternatively some noa-bonding electrons may not te relevant to fluorescence quenching.) Decreases in fluorescence yield are associated with red shifts in the fluorescence maximum, and in the solvents of highest polarity the fluorescence yield is again small indicating that glycerol and water can enhance radiationless tunneling—presumably by altering Franck-Condon configurations and/or improving electronic-vibrational coupling between solute and solvent. The quantum yield is uniform throughout the atsorption band for a given solvent, but studies in aqueous buffers varying from pH 1 to 11 show that the fluorescence yield is greater for charged than for neutral molecules. Further, the fluorescence excitation peak is red shifted in powders. Since phosphorescence is the predominant emission at 777deg;K and increases in fluorescence can be correlated with the presumed solvation of non-bonding electrons, the singlet excited state of lowest energy in ‘unperturbed’ purine must be n-π* in nature. The shape of the phosphorescence band and the decay lifetime of ? 1 sec at 77°K lead to the conclusion that the emitting triplet is a π-π* state. The eight vibrational structures in phosphorescence emission can be readily grouped into two progressions: there is an average separation of about 1300 cm^-1 between peaks within a given progression, and the two sets are mutually displaced by about 500 cm-^l. Individual vibrational peaks are favoured in different solvents and the whole band may be shifted up to 500 cm^-l. Even larger shifts are observed in charged purine molecules and in powders (up to 3000 cm^-l) and the presumed 0–0 band is not observed.     

UV-visible absorption spectra and luminescence of the pesticide fenarimol

The UV-visible absorption and emission spectra have been measured of the pesticide fenarimol ((±)-2,4′-dichloro-α-(pyrimidin-5-yl)-benzhydryl alcohol) in solution. From comparison with the spectra of chlorotoluenes and pyrimidine, and from the effect of solvent polarity on the absorption spectrum, it is shown that the lowest excited singlet state is localized on the pyrimidine ring, and has n,π* character. Higher excited π,π* states are localized on both chlorotoluene and pyrimidine rings. Fenarimol shows a weak, fluorescence from the n,π* state, with a quantum yield which is strongly dependent on solvent. It is shown that this is due to changes in the nonradiative decay rate, particularly in protic solvents, due to increased intersystem crossing. Phosphorescence is observed in low temperature glasses. Although this shows two decay components, it is suggested that only one triplet state is involved, and that this has predominantly π,π* character.     

Dual phosphorescence from 5-methylbicyclo[4.3.01,5]non-1-en3-one

Phosphorescence has been simultaneously observed from both a ³π, π* and a ³n,π* level of 5-methylbicyclo-[4.3.0^1,5non-1-en-3-one. The emission from the higher energy ³n,π* state, which is in thermal equilibrium with the ³π,π* state, is quenched by lowering the temperature and also quenched by increasing the solvent polarity so as to raise the energy of the ³n,π* state relative to the ³π,π* state.     

Solvent and Substituent Effects on the Spectra of Some Substituted Thioureas

A study on the effect of a number of solvents, covering a broad polarity range i.e. from dioxane (D=2.20) to acetonitrile (D=38.0), has been made on the electronic transitions of N-aryl, N′-2-(5-halo-pyridyl) thioureas (where aryl= -C₂H₅ or O-CH₃-C₆H₅-, and halo= -Cl, -Brand -I). Two intense absorption maxima in the regions 270-285 nm (assigned for thiocarbonyl π-π* transition) are exhibited by all the substituted thioureas studied. The excitation energies and oscillator strengths of these transitions have been calculated. A correlation between ‘E_T’ and ‘Z’ (an empirical measure of solvent polarity) has been attempted. Solvent sensitivities of these compounds have also been calculated. The effect of halo-substituents, in the pyridine ring, on the spectra of these substituted thioureas has also been studied. It has been proposed that there is a delocalization of electrons between the pyridine ring and the thiourea unit of these compounds. This delocalization of electronic charge is affected by the substitution of the halo-groups in the pyridine ring at para position to the thiourea unit which is reflected in the intensities and shifting of the absorption maxima.     

Ultrafast dynamics of the excited states of 1-(p-nitrophenyl)-2-(hydroxymethyl)pyrrolidine

The dynamics of the excited states of 1-(p-nitrophenyl)-2-(hydroxymethyl)pyrrolidine (p-NPP) has been investigated using the subpicosecond transient absorption spectroscopic technique in different kinds of solvents. Following photoexcitation using 400 nm light, conformational relaxation via twisting of the nitro group, internal conversion (IC) and the intersystem crossing (ISC) processes have been established to be the three major relaxation pathways responsible for the ultrafast deactivation of the excited singlet (S(1)) state. Although the nitro-twisting process has been observed in all kinds of solvents, the relative probability of the occurrence of the other two processes has been found to be extremely sensitive to solvent polarity, because of alteration of the relative energies of the S(1) and the triplet (T(n)) states. In the solvents of lower polarity, the ISC is predominant over the IC process, because of near isoenergeticity of the S(1)(ππ*) and T(3)(nπ*) states. On the other hand, in the solvents of very large polarity, the energy of the S(1)(ππ*) state becomes lower than those of both the T(3)(nπ*) and T(2)(nπ*/ππ*) states, but those of the T(1)(ππ*) state and the IC process to the ground electronic (S(0)) state are predominant over the ISC, and hence the triplet yield is nearly negligible. However, in the solvents of medium polarity, the S(1) and T(2) states become isoenergetic and the deactivation of the S(1) state is directed to both the IC and ISC channels. In the solvents of low and medium polarity, following the ISC process, the excited states undergo IC, vibrational relaxation, and solvation in the triplet manifold. On the other hand, following the IC process in the Franck-Condon region of the S(0) state, the vibrationally hot molecules with the twisted nitro group subsequently undergo the reverse nitro-twisting process via dissipation of the excess vibrational energy to the solvent or vibrational cooling.     

An experimental and theoretical study of excited-state dipole moments of some flavones using an efficient solvatochromic method based on the solvent polarity parameter, E(N)(T)

The electronic absorption and fluorescence spectra of some biologically active natural flavones have been recorded at room temperature (298 K) in solvents of different polarities. The effects of the solvents upon the spectral properties are discussed. Difference in fluorescence intensity of flavones has been explained on the basis of intersystem crossing and degree of non-planarity calculated theoretically using Austin Model 1 (AM1) method. Excited-state dipole moments have been determined using the solvatochromic method based on the microscopic solvent polarity parameter, E(N)(T). A reasonable agreement has been observed between experimental and AM1 calculated dipole moment changes. Our results are found to be quite reliable in view of the fact that the correlation of the solvatochromic Stokes shifts with microscopic solvent polarity parameter, E(N)(T) is superior to that obtained using bulk solvent polarity functions for all the systems studied here.     

N-(2,2,6,6-四甲基-4-哌啶基-1-氧)-N＇-芳酰氨基硫脲EPR波谱的溶剂效应

本文研究了五种哌啶类稳定氮氧自由基在九种极性不同的溶剂 中EPR谱特性。观察到超精细分裂常数A~N与Kosower Z值、Reichardt E~T值之间存在良好的线性关系。同时还发现=N_O共轭键在外磁场作用下所产生的三组裂磁能中每两组相邻能级的能量差ΔE、氮原子上的π电子自旋密度P^x~N值与Z、E~T值也有良好的线性关系。以及自由基旋转相关时间τ、高场峰相对高度h~r与溶剂粘度η值之间也呈线性关系。