吸附于AgCl溶胶表面的单羟基四苯基卟啉的电子吸收光谱

研究了两种单取代羟基四苯基卟啉——— 5 - (4-羟基苯基 ) - 10 ,15 ,2 0 -三苯基卟啉 (H2 POH)和 5 - (4-羟基苯基 ) - 10 ,15 ,2 0 -三氯苯基卟啉 (H2 (p -Cl) 3 POH)在冰醋酸中和吸附于AgCl溶胶表面的电子吸收光谱(UVA)和化学反应 .结果表明 ,在冰醋酸中H2 POH和H2 (p -Cl) 3 POH均以二酸和游离碱的形式存在 ;在乙醇中 ,pH值为 10 .5 - 11.5时 ,H2 POH与H2 (p -Cl) 3 POH在AgCl表面发生配位反应 ,生成了Ag(Ⅱ )POH和Ag(Ⅱ ) (p -Cl) 3 POH ,并且溶液的酸度越低 ,配位反应的速度越大     

酸度对AgCl溶胶表面吸附H2TPP化学反应的影响

讨论了ｍｅｓｏ四苯基卟啉（Ｈ２ＴＰＰ）吸附在ＡｇＣｌ溶胶表面的吸收光谱。实验表明,当ｐＨ＝２．０～６．０时,Ｈ２ＴＰＰ吸附于ＡｇＣｌ溶胶表面以卟啉二酸Ｈ４ＴＰＰ２＋存在;当ｐＨ＝６．７５～１１．０时,Ｈ２ＴＰＰ吸附于ＡｇＣｌ溶胶表面发生络合反应,生成二价银络合物Ａｇ（Ⅱ）ＴＰＰ,并且络合反应的速率随ｐＨ值的增大而加快。     

酸度对AgCl溶胶表面吸附H2TPP的化学反应的影响

讨论了ｍｅｓｏ－四苯基卟啉（Ｈ２ＴＰＰ）吸附在ＡｇＣｌ溶胶表面的吸收光谱。实验表明,当ｐＨ＝２．０￣６．０时,Ｈ２ＴＰＰ吸附于ＡｇＣｌ溶胶表面以卟啉二酸Ｈ４ＴＰＰ＾２＋存在;当ｐＨ＝６．７５￣１１．０时,Ｈ２ＴＰＰ吸附于ＡｇＣｌ溶胶表面发生络合反应,生成二阶银络合物Ａｇ（Ⅱ）ＴＰＰ,并且络合反应的速率随ＰＨ值的增大而增快。     

H4TPP^2＋吸附在Ag溶胶表面的吸收光谱

本文研究了５，１０，１５，２０－四苯基中啉二酸吸附在Ａｇ溶胶表面的吸收光谱。发现Ｈ４ＴＰＰ＾２＋吸附在Ａｇ溶胶表面的去质子化现象，生成游离碱卟啉Ｈ２ＴＰＰ，随样品放置时间延长，卟啉分子进一步发生络合反应，生成Ａｇ（Ⅱ）ＴＰＰ。对络合反应的过程和机理进行了讨论。     

对位取代的四苯基卟啉衍生单酸的合成及有关的结构理论

报导了对位取代的四苯基卟啉衍生单酸的合成及表征,阐述了一些有关共轭卟啉平面环体系的结构理论。     

酸度对AgCl溶胶表面吸附H2TPP化学反应的影响

讨论了meso-四苯基卟啉(H     

薄层色谱法分离四苯基卟啉和四苯基钴卟啉

提出了用薄层色谱分离四苯基卟啉和四苯基钴卟啉的方法.方法中以石油醚-二甲苯(体积比为2:1)二元溶剂体系为展开剂,在硅胶薄层板上分离了四苯基卟啉和四苯基钴卟啉,所得斑点清晰、无拖尾.应用此薄层色谱法跟踪检测了四苯基钴卟啉的合成.     

影响间位取代四苯基卟啉锌轴向配合物稳定因素的研究

用光度滴定法研究了间位取代四苯基卟啉锌[ZnT(m-X)PP,X=NO₂,Cl,OCH₃,H,CH₃]与3种新型空间不对称金属席夫碱和4种取代咪唑的轴向配位反应动力学.采用Rose-Drago数据处理方法确定了各反应体系的平衡常数,探讨了温度、轴向配体、卟啉环上的取代基对轴向配合物稳定性的影响,发现在5种间位取代四苯基卟啉锌与7种轴向配体的配位反应中均存在线性自由能关系和等平衡关系,对所研究体系采用不同的方法求取等平衡温度β及温度T→∞时的反应对电子效应的敏感系数ρ_∞,得到吻合的结果.     

四苯基卟啉及其衍生物的结构与性质的研究（V）：氨基取代四…

本文首先确定卟吩的同系序数（ｎ）和氨基取代四苯基卟啉衍生物的同系序数（Ｎ），然后将同系因子（１／２）＾２＾／＾Ｎ与其电子活动性能（Ｙ）作线拟合，得到一组同系线性方程：Ｙ＝ａ＋ｂ．（１／２）＾２＾／＾Ｎ其中，ａ，ｂ是与Ｙ有关的常数，并用同系线性规律解释了λｍａｘ红移现象，得出了一些规律性的结论。     

尾式亮氨酸四苯基卟啉锌与嘧啶轴配反应光谱和热力学

研究了 5 - (4′ -亮氨酸丁氧苯基 ) - 10 ,15 ,2 0 -三苯基卟啉锌 (Zn[Leu -TPP])与嘧啶 (L)在氯仿溶液中轴配反应光谱和热力学性质 .用紫外 -可见分光光度法确定了轴向配位反应体系的配位数 (n)和平衡常数K .用温度系数法求得了轴配反应的标准摩尔焓变ΔrH m 和标准摩尔熵变ΔrS m .探讨了温度对轴向配位反应反应的影响 .     

Calculation of activation-controlled reaction rate constants from parameters of electronic absorption spectra of ion pairs

An equation relating the rate constants of a bimolecular activation-controlled redox reaction to the parameters directly determined from the electronic absorption spectra was obtained in the framework of the Marcus-Hush theory. Applicability of the equation for the prediction of redox reaction rate constants was shown. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No.6, pp. 1007–1010, June, 2000.     

呋喃查尔酮结构与电子光谱的密度泛函理论研究

在密度泛函理论的PBE1PBE/6-31G(d)水平上对呋喃查尔酮及其衍生物的几何结构进行优化计算.在获得基态稳定结构的基础上,应用含时密度泛函理论计算其电子吸收光谱,探讨了取代基和溶剂对电子吸收光谱的影响,计算结果与实验结果吻合很好,平均绝对偏差仅为3.3nm(0.04eV).结果表明,取代基的引入和溶剂极性的增大均使光谱发生红移.通过前线轨道分析,揭示了该类化合物的主要吸收峰均源自分子中HOMO→LUMO电子跃迁.     

Synthesis and electronic spectra of dimeric phthalocyanines

Dimeric phthalocyanines of a new type with a bridging 9,9,10,10-tetramethyl-9,10-dihydroanthracene fragment were synthesized. On the basis of X-ray diffraction analysis and molecular modeling of 9,9,10,10-tetramethyl-9,10-dihydroanthracene, a nearly planar structure was assumed for these phthalocyanines. The electronic absorption spectra of the obtained phthalocyanines and their monomeric and conjugated dimeric analogs were compared. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1686–1692, October, 2006.     

Computer simulation of band shapes in electronic absorption spectra of dimers of organic dyes

The band shapes in the absorption spectra of dimers of cyanine dyes were simulated using a combination of an empirical molecular force field for the ground state with quantum-chemical calculations of the electron excitation energy as a function of normal nuclear coordinates. The shape and the width of an absorption band strongly depend on the mutual arrangement of the monomers. If the monomers are located one directly above the other, the sublevels arising from intramolecular vibrations disappear in the spectrum, and a large hypsochromic shift of the 0-0-transition band is observed, which results mainly from through-space interaction of monomer orbitals. If the monomers are strongly shifted relative to each other, the sublevels mentioned are also absent in the spectrum, but the bathochromic shift of the 0-0-transition band is small and results from interaction of dipole moments of electron transitions. A rather broad region of intermediate structures is found between these dimer forms, where the interaction of dipole moments of electron transitions in monomers is low, and the shapes of absorption bands are similar to those of the monomers.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1705–1710, September, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-08539) and the International Science Foundation (Grant M1Z 000).     

Time‐dependent density functional theory studies of the electronic absorption spectra of metallophthalocyanines of group IVA

Time‐dependent density functional theory (TD‐DFT) calculations were carried out in a comparative study of the electronic absorption spectra of lead(II) phthalocyaninate (PbPc), tin(II) phthalocyaninate (SnPc), tin(IV) dichlorophalocyaninate (PcSnCl₂), germanium(II) phthalocyaninate (GePc), and germanium (IV) dichlorophalocyaninate (PcGeCl₂) with the B3LYP method and LANL2DZ basis set. Our calculated bands correspond well with the experimental results. The electronic natures of all the bands in the absorption spectra are assigned and analyzed comparatively according to the calculated electronic transition contributions. With the increase of the dielectric constant from CHCl₃ to DMSO, all the electronic absorption bands are somewhat red shift, consistent with the shift rules measured experimentally. The radius of the central metals has great influence to the absorption spectra, especially for the B bands. The influence of the radius of the central metals to the absorption spectra of PcSnCl₂ and PcGeCl₂ is smaller than to the spectra of the nonplanar MPcs (M = Pb, Sn, and Ge). Axial ligands also greatly changed the electronic absorption spectra due to the change of the orbital energy level and the molecular symmetry. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

二芳杂环基乙烯的合成及其光致变色反应研究

本文报道了2,3-双 (1,2-二甲基-3-吲哚基)-2-丁烯 (DF1),2,3-双 (1,4-二苯基-2-甲基-3-吡咯基)-2-丁烯 (DF2), 2,3-双(1-对甲苯基-4-苯基-2-甲基-3-吡咯基)-2-丁烯 (DF3), 2,3-双(1-对溴苯基-4-苯基-2-甲基-3-吡咯基)-2-丁烯 (DF4) 和2,3-双 (1-对甲氧苯基-5-苯基-2-甲基-3-吡咯基)-2-丁烯 (DF5) 的合成,以及它们的光致变色行为的研究。特别是DF1和DF5的光呈色和光消色过程进行了较为细致的研究。     

Spectroscopic studies of the autocomplex type compounds 1. Use of spectrophotometry derivatives for interpretation of electronic spectra of autocomplexes of the picramide series

The complicated electronic absorption spectra of several picramide autocomplexes were interpreted by the second derivative spectrophotometric method. A linear correlation was established between the values of the intramolecular charge-transfer energy and the ionization potential of a donor fragment of molecules. The ionization potentials of several compounds were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1188–1191, May, 1996.     

Theoretical study on the structures and electronic spectra of C120On (n=1,2)

ZINDO series calculations have been carried out to study the double‐cage oxides C₁₂₀O_n (n=1,2). The results show that the formation of a furan ring by the bridge‐bond between the two cages connected the two C₆₀ fullerene units and formed the C₁₂₀O with C_2v symmetry. C₁₂₀O₂ has two isomers with C_2v symmetry depending on either 6–6 or 6–5 connection between the two cages. Two furan rings and a pure four‐member ring form in this molecule. The formation of C₁₂₀O assuages the constraint of epoxide structure in C₆₀O, shortens the distance of the monomers, and produces some finite interaction between the two balls. More bonding in C₁₂₀O₂ shortens the distance of the two cages further and brings about stronger interaction. However, the two cages in C₁₂₀O_n (n=1,2) behave somehow independently that the electronic spectra of C₁₂₀O_n (n=1,2) are similar to those of C₆₀. The 6–6 connection isomer of C₁₂₀O₂ is more stable; its spectra are in good agreement with those of the experiment. The calculated electronic spectra of C₁₂₀O not only are in good agreement with the experiment in the ultraviolet region but also get some weak peaks in the visible region (>400 nm) not observed in experiment. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 291–307, 2000     

The structures and electronic absorption spectra of substituted phenyldiacetylenes: experimental and theoretical studies

The results of experimental and theoretical investigation of the electronic absorption spectra of substituted phenyldiacethylenes are presented. The bands in the experimental spectra were assigned in detail using quantum chemical calculations of the electronic structures and spectra of the molecules. The influence of the interaction of the substituents on the spectral parameters of the systems under study was analyzed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1947–1953, October, 2007.