以偶氮苯基团为周边取代基的锌酞菁的合成及光物理性质

合成了两种带有偶氮苯周边取代基的锌酞菁化合物,并对其进行了结构表征.与一般酞菁的吸收光谱相比,偶氮苯酞菁的UV-Vis光谱的B带吸收峰强度明显强于Q带.该类化合物在光照条件下表现出重复性较好的顺反异构化性质.Z-扫描结果表明,这类化合物的三阶非线性光学性能主要来源于酞菁的非线性折射率,且β位取代的酞菁的三阶非线性效应大于α位取代的,顺反异构对酞菁的三阶非线性光学性能的影响不大.     

Homo‐ and Heteroleptic Phototoxic Dinuclear Metallo‐Intercalators Based on RuII(dppn) Intercalating Moieties: Synthesis,Optical, and Biological Studies

Using a new mononuclear “building block,” for the first time, a dinuclear Ru^II(dppn) complex and a heteroleptic system containing both Ru^II(dppz) and Ru^II(dppn) moieties are reported. The complexes, including the mixed dppz/dppn system, are ¹O₂ sensitizers. However, unlike the homoleptic dppn systems, the mixed dppz/dppn complex also displays a luminescence “switch on” DNA light‐switch effect. In both cisplatin sensitive and resistant human ovarian carcinoma lines the dinuclear complexes show enhanced uptake compared to their mononuclear analogue. Thanks to a favorable combination of singlet oxygen generation and cellular uptake properties all three of the new complexes are phototoxic and display potent activity against chemotherapeutically resistant cells.     

Chirogenesis in Zinc Porphyrins: Theoretical Evaluation of Electronic Transitions,Controlling Structural Factors and Axial Ligation

In the present work, sixteen different zinc porphyrins (possessing different meso substituents) with and without a chiral guest were modelled using DFT and TD-DFT approaches in order to understand the influence of various controlling factors on electronic circular dichroism (ECD) spectra. Two major aspects are influenced by these factors: excitation energy of the electronic transitions and their intensity. In the case of excitation energy, the influence increases in the following order: orientation of the peripheral substituents<substituent's nature<axial ligation. However, the deformation of the porphyrin plane does not affect the excitation energies. In the case of intensity, the influence increases as follows: substituent's nature<conrotatory orientation of the peripheral substituents<deformation of the porphyrin plane<disrotatory orientation of the peripheral substituents<axial ligation.     

1,2,5-Triarylcycloalka[c]arsoles: Structural Effects of Fused-cycloalkanes on Stability and Photophysical Properties

Herein, we have synthesized a variety of cycloalkane-fused arsoles. Cyclopentane and cyclohexane were incorporated into the cycloalkane-fused arsoles. Surprisingly, cyclohexane-fused arsole 2 a gradually decomposed via oxidative ring-opening under ambient conditions, while cyclopentane-fused 1 a was stable. In addition, the Stokes shift of 2 a (7766 cm⁻¹) is larger than that of 1 a (5120 cm⁻¹). The effects of the fused cycloalkane on the stability and photophysical properties were attributed to the distortion of the cycloalkane. Computational calculations demonstrated that the cyclohexane moiety in 2 a was frustrated upon being incorporated into the rigid arsole ring, while the cyclopentane moiety in 1 a was much less distorted.     

水分子团簇结构的改变及其生物效应

概述了近30年来从水分子团簇结构的发现到水分子簇的稳定结构及相关理论计算的研究进展;总结了改变水分子团簇结构的四种方法．包括外加磁场、外加电场、激光辐射以及直接加热法．分别讨论了这四种方法的作用机理;最后简要介绍了改变水分子团簇结构所诱发的生物效应,并对该领域的研究前景作了展望。     

Structural,Vibrational and Electronic Properties of Defective Single‐Walled Carbon Nanotubes Functionalised with Carboxyl Groups: Theoretical Studies

Covalent sidewall functionalisation of defective zigzag single‐walled carbon nanotubes [SWCNTs(10,0)] with COOH groups is investigated by using DFT. Four types of point defects are considered: vacancy (V), divacancy [V₂(5‐8‐5), V₂(555‐777)], adatom (AA) and Stone–Wales (SW). The energetic, structural, electronic and vibrational properties of these systems are analysed. Decreasing reactivity is observed in the following order: AA>V>V₂(555‐777)>V₂(5‐8‐5)>SW. These studies also demonstrate that the position in which a carboxyl group is attached to a defective SWCNT is of primary importance. Saturation of two‐coordinate carbon atoms in systems with the vacancy V‐7 and with the adatom AA‐1(2) is 3.5–4 times more energetically favourable than saturation of three‐coordinate carbon atoms for all studied systems. Vibrational analysis for these two systems shows significant redshifts of the ν(C?O) stretching vibration of 96 and 123 cm^?1 compared to that for carboxylated pristine systems. Detailed electronic‐structure analysis of the most stable carboxylated systems is also presented.     

Substituents Effects to the Electrochemical,and In Situ Spectroelectrochemical Behavior of Metallophthalocyanines: Electrocatalytic Application for Hydrogen Evolution Reaction

This study describes the effects of the number of fluoro substituents to the electrochemical, in situ spectroelectrochemical, and electrocatalytic activities of metallophthalocyanines for the hydrogen evolution reaction. Tuning of the number of fluoro groups shifts the redox processes and affects the aggregation tendencies of the complexes. An in situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. Cobalt phthalocyanines incorporated into Nafion film on a glassy carbon electrode decreases the overpotential of the working electrode for H⁺ reduction. The number and position of the electron withdrawing substituents and nature of the metal center change the electrocatalytic activities for the hydrogen evolution reaction in aqueous solutions.     

Synthesis, Photophysical and Electrochemical Characterization of the Heteroleptic Iridium Complexes with Modified Ancillary Ligand by Carrier-transporting Groups

Two heteroleptic iridium complexes with a general formulation of (piq)₂Ir(G‐pic) were synthesized and characterized by ¹H NMR, ¹³C NMR and element analysis, in which piq is 1‐phenylisoquinoline, G‐pic is picolinic acid derivative containing carrier‐transporting group by a non‐conjugated connection of 1,6‐dioxyhexane. Both (piq)₂Ir(G‐pic) complexes exhibited an enhanced UV absorption band at 310–400 nm, an increased HOMO energy level and an identical red emission peaked at 612 nm with higher fluorescence quantum efficiency (ø_f), compared to (piq)₂Ir(pic) in dichloromethane solution. Interestingly, this iridium complex containing both hole‐transporting triphenylamine and electron‐transporting oxadiazole moieties exhibited the best Ф_f of 0.58 using Ru(bpy)₃(PF6)₂ as the reference (ø_f=0.062 in acetonitrile). This work indicates that incorporating carrier‐transporting groups into ancillary ligand by a non‐conjugated connection is available for improving the optophysical properties of their iridium complexes.     

Expanded Pyridiniums: Bis‐cyclization of Branched Pyridiniums into Their Fused Polycyclic and Positively Charged Derivatives—Assessing the Impact of Pericondensation on Structural,Electrochemical, Electronic,and Photophysical Features

This study evaluates the impact of the extension of the π‐conjugated system of pyridiniums on their various properties. The molecular scaffold of aryl‐substituted expanded pyridiniums (referred to as branched species) can be photochemically bis‐cyclized into the corresponding fused polycyclic derivatives (referred to as pericondensed species). The representative 1,2,4,6‐tetraphenylpyridinium ( 1^H ) and 1,2,3,5,6‐pentaphenyl‐4‐(p‐tolyl)pyridinium ( 2^Me ) tetra‐ and hexa‐branched pyridiniums are herein compared with their corresponding pericondensed derivatives, the fully fused 9‐phenylbenzo[1,2]quinolizino[3,4,5,6‐def]phenanthridinium ( 1^H f ) and the hitherto unknown hemifused 9‐methyl‐1,2,3‐triphenylbenzo[h]phenanthro[9,10,1‐def]isoquinolinium ( 2^Me f ). Combined solid‐state X‐ray crystallography and solution NMR experiments showed that stacking interactions are barely efficient when the pericondensed pyridiniums are not appropriately substituted. The electrochemical study revealed that the first reduction process of all the expanded pyridiniums occurs at around ?1 V vs. SCE, which indicates that the lowest unoccupied molecular orbital (LUMO) remains essentially localized on the pyridinium core regardless of pericondensation. In contrast, the electronic and photophysical properties are significantly affected on going from branched to pericondensed pyridiniums. Typically, the number of absorption bands increases with extended activity towards the visible region (down to ca. 450 nm in MeCN), whereas emission quantum yields are increased by three orders of magnitude (at ca. 0.25 on average). A relationship is established between the observed differential impact of the pericondensation and the importance of the localized LUMO on the properties considered: predominant for the first reduction process compared with secondary for the optical and photophysical properties.     

Desymmetrizing Heteroleptic [Cu(P^P)(N^N)][PF6] Compounds: Effects on Structural and Photophysical Properties,and Solution Dynamic Behavior

The preparation, characterization and electrochemical and photophysical properties of a series of desymmetrized heteroleptic [Cu(P^P)(N^N)][PF₆] compounds are reported. The complexes incorporate the chelating P^P ligands bis(2-(diphenylphosphanyl)phenyl)ether (POP) and (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (xantphos), and 6-substituted 2,2′-bipyridine (bpy) derivatives with functional groups attached by –(CH₂)_n– spacers: 6-(2,2′-bipyridin-6-yl)hexanoic acid (1), 6-(5-phenylpentyl)-2,2′-bipyridine (2) and 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-2,2′-bipyridine (3). [Cu(POP)(1)][PF₆], [Cu(xantphos)(1)][PF₆], [Cu(POP)(2)][PF₆], [Cu(xantphos)(2)][PF₆], and [Cu(xantphos)(3)][PF₆] have been characterized in solution using multinuclear NMR spectroscopy, and the single crystal structure of [Cu(xantphos)(3)][PF₆]^.0.5Et₂O was determined. The conformation of the 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-substituent in the [Cu(xantphos)(3)]⁺ cation is such that the α- and β-CH₂ units reside in the xanthene ‘bowl’ of the xantphos ligand. The 6-substituent desymmetrizes the structure of the [Cu(P^P)(N^N)]⁺ cation and this has consequences for the interpretation of the solution NMR spectra of the five complexes. The NOESY spectra and EXSY cross-peaks provide insight into the dynamic processes operating in the different compounds. For powdered samples, emission maxima are in the range 542–555 nm and photoluminescence quantum yields (PLQYs) lie in the range 13–28%, and a comparison of PLQYs and decay lifetimes with those of [Cu(xantphos)(6-Mebpy)][PF₆] indicate that the introduction of the 6-substituent is not detrimental in terms of the photophysical properties.