不对称双席夫碱过渡金属配合物的电子光谱和非线性光学性质的理论研究

本文采用密度泛函理论中的M05方法对比研究了一类双席夫碱及其衍生物与金属Co、Ni和Cu配位后配合物的结构,非线性光学性质以及激发态性质.结果表明,Co配合物的三重态,Ni配合物的二重态以及Cu配合物的单重态为最佳稳定结构.通过最佳稳定结构计算得到的配合物非线性光学性质表明,三种金属配合物中Cu配合物表现出较高的一阶和二阶超极化率.通过对其激发态性质分析表明在配体苯环上引入甲氧基使电子跃迁种类减少,导致超极化率下降,非线性光学性质减弱.     

不对称双席夫碱过渡金属配合物的电子光谱和非线性光学性质的 理论研究

本文采用密度泛函理论中的M05方法对比研究了一类双席夫碱及其衍生物与金属Co、Ni和Cu配位后配合物的结构,非线性光学性质以及激发态性质. 结果表明,Co配合物的三重态,Ni配合物的二重态以及Cu配合物的单重态为最佳稳定结构. 通过最佳稳定结构计算得到的配合物非线性光学性质表明,三种金属配合物中Cu配合物表现出较高的一阶和二阶超极化率. 通过对其激发态性质分析表明在配体苯环上引入甲氧基使电子跃迁种类减少,导致超极化率下降,非线性光学性质减弱.     

铒有机配合物的合成、表征与近红外发光性能研究

合成了乙酰基丙酮(AcAc)和二苯甲酰基甲烷(DBM)的水合二元铒配合物以及乙酰基丙酮、二苯甲酰基甲烷和三氟乙酰基丙酮(TFA)分别与1,10-邻菲罗啉(Phen)的三元铒配合物,并经元素分析确认;表征了配合物的紫外-可见吸收光谱和红外吸收光谱;探讨了铒配合物的近红外发光性能,并对不同配体对发光性能的影响进行分析比较。结果表明Er(AcAc)₃Phen三元配合物是所研究的几种配合物中近红外发光性能最优的。     

Halide-ion conductivities of the complexes of cryptand[2.2.2] with alkali-metal halides and alkaline earth metal halides

Halide ion conductivities of the complexes of cryptand[2.2.2] with alkali-metal halides or alkaline-earth metal halides were measured at 20–160°C. The halide ion conductivities of the complexes were found to be much higher than those of the crown ether complexes with alkali-metal halides or alkaline-earth metal halides. This is caused by the much weaker Coulomb attraction between metal-cation and halide ion in cryptand complexes than in crown ether complexes.     

FTIR法研究氨基酸稀土配合物与磷脂的相互作用

利用傅里叶变换红外光谱（ＦＴＩＲ）法研究了不同类型氨基酸及其配合物与二棕榈酰磷脂酰胆碱脂质体浇铸膜的相互作用。结果表明，在有氨基酸存在下，二棕榈酰磷脂酰胆碱的红外谱图没有明显的变化；氨基酸稀土配合物与磷脂极性头基团有静电相互作用，作用的程度随稀土离子、氨基酸及稀土同氨基酸配比的不同而有所不同。     

Optical anisotropy of liquid-crystal lanthanide complexes

Refractive and optical anisotropy indices have been measured for a number of liquid-crystal lanthanide complexes with different counter ions, ligands, and complexing agents. The optical anisotropy of the complexes is found to range from 0.002 to 0.09, i.e., to be one to two orders of magnitude smaller than that of classical calamitic liquid crystals. Analysis of the chemical structure of mesogenic complexes showed that the complexes containing counter ions with sizes much smaller than the ligand sizes and mixed-ligand complexes containing less than five ligands exhibit the largest optical anisotropy. The optical anisotropy of other mixed-ligand complexes with a large number of ligands is much smaller. The reason is the different degrees of anisometry of complexes and, as a consequence, the difference in the polarizability anisotropy and, correspondingly, the optical anisotropy of the mesophase.     

Switchable molecular magnets

Various molecular magnetic compounds whose magnetic properties can be controlled by external stimuli have been developed, including electrochemically, photochemically, and chemically tunable bulk magnets as well as a phototunable antiferromagnetic phase of single chain magnet. In addition, we present tunable paramagnetic mononuclear complexes ranging from spin crossover complexes and valence tautomeric complexes to Co complexes in which orbital angular momentum can be switched. Furthermore, we recently developed several switchable clusters and one-dimensional coordination polymers. The switching of magnetic properties can be achieved by modulating metals, ligands, and molecules/ions in the second sphere of the complexes.     

Fluorescence of Metal–Ligand Complexes of Mono- and Di-Substituted Naphthalene Derivatives

In this work, metal ion complexes for several naphthalene derivatives have been investigated. Different working pH values were chosen: 2.5 for complexes with Zr(IV), 4.0 for complexes with Fe(III), 5.0 for complexes with Al(III), and 7.5 for complexes with Cu(II). A stoichiometry of 1:1 for all complexes except two has been established by use of the Benesi–Hildebrand method and the stability constants have been calculated. All complexes between naphthalene derivatives and Cu(II) and Fe(III) show fluorescence quenching. In the case of Al(III), all complexes provided enhanced fluorescence. For Zr(IV), only the complex with 3-hydroxy-2-naphthoic acid provided enhanced fluorescence. The value of the stability constants as a function of the substituents of naphthalene derivatives has been analyzed. One can conclude that Cu(II) showed the largest binding affinity for the mono-substituted derivatives. However, Al(III) and Zr(IV) produced greater selectivity for the di-substituted derivatives. Iron(III) showed no specific binding with any of the naphthalene derivatives.     

邻苯二甲酸—邻菲罗啉—铕—铽络合体系的荧光性能研究

波长为３６５ｎｍ的紫外光激发下均可发出特征荧光的邻苯二甲酸－邻菲罗啉－铕和铽固体络合物以机械研磨和化学作用两种方式进行混合，研究了这两系列混合络合物的荧光光谱和红外光谱。结果表明，由于铕、铽之间存在相互影响，其荧光强度变化较大，而荧光发射峰位基本不变。经化学混合后铽对铕的荧光强度有极强的敏化作用，铕对铽具有很强的猝灭作用，并用红外光谱对上述四种络合物体系的结构进行了表征     

金属络合物分子间交换反应的核磁共振研究Ⅲ.噻吩甲酰三氟丙酮铝与苯甲酰丙酮铝体系分子间配体交换的19F NMR研究

用¹⁹F NMR研究了噻吩甲酰三氟丙酮铝与苯甲酰丙酮铝体系分子间的团体交换反应,求得了交换反应的平衡常数及自由能,结果表明交换反应有利于混合配体络合物生成,平衡时混和溶液中各组分分布偏离统计分布。     

Spectral-luminescence study of the formation of QD-sulfophthalocyanine molecule complexes in an aqueous solution

The spectral-luminescence manifestations of the formation of quantum dot (QD)-phthalocyanine complexes as a result of electrostatic interaction have been investigated. Effective QD luminescence quenching has been found in complexes of this type. The luminescence of the molecules associated in complexes with QDs is also partially quenched. A mathematical model of the formation of QD-organic molecule complexes is proposed.     

Energy transfer between lanthanide ions in nanostructures of their complexes. I

We study the regular features of the behavior of the intensity I _lum and the luminescence decay time τ _lum of complexes of Eu and Tb ions with several β-diketones and 1,10-phenanthroline in the case where these complexes from nanostructures with complexes of lanthanide ions that are electronic excitation acceptors of these Eu and Tb ions. The composition of mixed nanostructures formed in a solution is shown to depend on the method of their preparation, on the ability of complexes to form mixed rather than homogeneous nanostructures, and on the concentration of complexes in the solution. We reveal that complexes of Yb, Tm, and Dy ions simultaneously increase I _lum and τ _lum of Eu complexes due to energy transfer through ligands of complexes and decrease the value of these quantities for Eu complexes due to energy transfer from Eu(III) ions to ions of Yb, Tm, and Dy. For all interacting complexes, the changes in I _lum and τ _lum of complexes of Eu (Tb) in the presence of complexes, energy acceptors, are shown to be determined by competition between two processes: a decrease in these quantities due to energy transfer between ions and their increase caused by an increase in the probability of nonradiative transitions in Eu (Tb) ions due to an increase in the size of structures. We propose a method of separation of these two processes.     

五种氨基酸钆络合物的ESR波谱

迄今未见任何稀土氨基酸络合物的ESR波谱报道,本文在合成Gd³⁺分别与甘氨酸、β-丙氨酸、谷氨酸、天冬氨酸和天冬酰胺五种氨基酸络合物的基础上,测定了不同温度下,水溶液、粉末及分子筛吸附样品的ESR谱,讨论了络合物中晶体场强,对称性及成键特性。     

Vibrational Spectra of Hydrogen Bonded Complexes Between Acetophenone and Some Phenol Derivatives

The hydrogen bonded complexes between hydroxylic derivatives and carbonyl bases have been extensively studied by infrared spectroscopy but meager Raman spectroscopic results are available for such complexes. This work reports on a study of the Raman intensity of the v_C[dbnd]0 stretching vibration of hydrogen bonded complexes formed between acetophenone and some phenol derivatives. The formation constants of these complexes are calculated from infrared spectroscopy.     

Comparison of Mid-IR with NIR in Polymer Analysis

Abstract

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) represents a powerful technique for analyzing biological samples due to the ultrahigh resolving power, high mass accuracy, and multiple-stage tandem mass spectrometry (MSⁿ). With the advent of electrospray ionization (ESI), determinations of binding stoichiometry and binding sites for protein complexes are available. This review summarizes the recent FT-ICR MS applications in characterization of protein complexes, such as protein-peptide complexes, protein-protein complexes, and protein-nucleic acid complexes. Especially, combined with ECD and SWIFT techniques, FT-ICR MS has unique ion manipulation capabilities and plays a critical role in the analysis of protein complexes.     

Intermolecular energy transfer between lanthanide complexes: 6. Influence of metal-to-ligand ratio on the transfer from terbium (III) to europium (III) complexes of L-histidine

The nature of the complexes formed between Tb³⁺ and L-histidine was investigated by making use of the fact that electronic energy can be absorbed by Tb³⁺/HIS complexes and subsequently transferred in a non-radiative manner to Eu³⁺/HIS complexes. The transfer was found to depend on the possible association of donor and quencher, and this information was used to outline the conditions under which the histidine complexes were found to self-associate. Supplementary information was obtained from measurements of the pH dependence of Tb³⁺ luminescence and differential absorbance spectra of Ho³⁺/HIS complexes. At low pH, the energy transfer occurred primarily by collisional means (implying the presence of monomeric complexes), whereas the transfer was governed by the formation of associated complexes at high pH.     

系列配合物的DNA光裂解及光谱性质的理论研究

用密度泛函理论,对系列钌多吡啶配合物1-3的电子结构、DNA光裂解及光谱性质进行了研究。首先,计算了配合物1-3的氧化还原电势,根据配合物1-3激发态还原电势的大小,合理地解释了配合物1-3的DNA光裂解能力。其次,根据配合物1-3的电子结构性质,设计了具有较高激发态还原电势的配合物4,从理论上预测配合物4具有较强的光裂解能力。最后,用TDDFT方法,在水溶液中对配合物1-3的电子吸收光谱进行了计算和模拟,计算得到的电子吸收光谱和实验结果吻合较好,实验上测得的较强吸收带从理论上被详细地解释,并研究了配合物的主配体对电子吸收光谱性质的影响。     

Competitive Trapping of Nitric Oxide (NO) Between Fe(III)-dithiocarbamate Complex and Liposome-encapsulated Trimethylammonio-PTIO: Effects of Ligand Structure, Charge on Liposome Surface, and External Pressure on NO-trapping Rates

Using a competitive nitric oxide (NO)-trapping method between Fe–dithiocarbamate (DTC) complexes and liposome-encapsulated 2-[4-trimethylammonio]-4,4,5,5-tetramethyl-imidazoline-1-oxyl 3-oxide (TMAPTIO), NO-trapping rates of Fe–DTC complexes in the presence of phosphatidylcholine liposomes were quantified for five kinds of Fe–DTC complexes. We investigated how the DTC ligand structure influences the NO-trapping rates of Fe–DTC complexes. The negatively charged liposomes give a higher NO-trapping rate of Fe–DTC complexes than do the positively charged ones, suggesting that the presence of a charge on the liposome surface affects the NO-trapping rate processes of Fe–DTC complexes. In addition, on the basis of the pressure dependence experiments for the competitive reaction, we evaluated the difference in activation volumes between the NO-trapping reactions by Fe–DTC complexes and TMA-PTIO, which allowed us to consider possible reaction mechanisms for the NO-trapping processes.     

Synthesis and characterization of highly fluorescent europium functionalized β-diketonate complexes

Several functionalized β-diketones and their europium complexes have been synthesized and characterized. The UV-Vis absorption, photoluminescent spectra, thermal and electrochemical properties of these complexes were investigated. The thermal analysis shows that the complexes have good thermal stability. By introducing the number of extended phenyl rings we succeeded in obtaining europium complexes with extremely high photoluminescent quantum yield (PLQY) in solution due to strong site isolation effect.     

Energy migration toward a dye in nanoparticles from complexes with short fluorescent state lifetimes

We have studied regular features of the fluorescence sensitization (cofluorescence) of coumarin 30 and rhodamine 6G introduced into nanoparticles from complexes Ln(PhBTA)₃phen, where PhBTA is p-phenylbenzoyltrifluoroacetone and Ln is a triply charged Pr, Nd, Sm, Eu, Er, or Yb ion, which absorbs in the fluorescence range of ligands of complexes and dyes. We show that both the cofluorescence intensities (I _cofl) of rhodamine 6G in nanoparticles from Sm and Eu complexes and the behavior of intensity I _cofl on the content of rhodamine 6G coincide with the corresponding data obtained for nanoparticles from La and Lu complexes doped with rhodamine 6G molecules. A considerable decrease in I _cofl of rhodamine 6G is observed only in nanoparticles from complexes Nd(PhBTA)₃phen. In nanoparticles from Pr, Nd, Sm, Eu, Er, and Yb complexes doped with coumarin 30, it has been observed that, depending on the choice of the central ion, I _cofl of coumarin 30 is 2 to 80 times lower compared to I _cofl of the dye in nanoparticles from La and Lu complexes. A separate analysis of the influence of these ions on the energy transfer from complexes to coumarin 30 and on the fluorescence intensity of coumarin 30 incorporated into nanoparticles from these ions showed that a decrease in I _cofl of coumarin 30 by a factor of 2?C20 occurs due to the reduction of ??_fl of ligands of complexes under the influence of the interaction with Pr, Nd, Sm, Eu, Er, and Yb ions. Since ??_fl of complexes La(PhBTA)3phen is ??2 ps, while that of complexes Gd(PhBTA)3phen is ??1 ps, then, in nanoparticles with a maximal decrease in I _cofl of coumarin 30, ??_fl of complexes is reduced to ??0.1 ps. It has been found that, in nanoparticles from complexes with this ??_fl, energy migration over complexes takes place. However, as distinct from nanoparticles from La, Lu, and Y complexes, the free path length of singlet excitons in nanoparticles from complexes of absorbing ions is smaller than the nanoparticle size.