[α-n-C_5H_(11)O]_4PcPd染料的溴化对性能的影响

合成了一种新的α位四戊氧基取代的钯酞菁 ,以其为原料作了不同程度的溴化反应并得到了一系列的酞菁染料溴化物 .实验证明 ,溴化后的酞菁染料最大吸收波长红移 ,摩尔消光系数降低 ,热稳定性也有所降低 ,热失重曲线发生了很大变化     

金属酞菁及其衍生物的紫外-可见光谱性能研究

用紫外-可见吸收光谱对金属酞菁及其衍生物进行研究,分析了酞菁的不同d电子数、不同价电子数和不同取代基对Q带和B带的影响。研究结果表明,d电子数增加,HOMO-LUMO分子轨道间能级差降低,电子光谱发生红移。金属酞菁中金属电荷对Q带影响不大,而随着电荷的增加,对B带有一定影响。Schiff基团的引入对Q带产生一定的影响,前线轨道能级裂分导致Q带红移并出现了不同程度的裂分。特别是二茂铁基团的酞菁金属配合物具有极高的非线性光学性能,有望开发成用于光动力诊疗的新型光敏剂。     

四邻苯二甲酰亚胺基金属酞菁的合成及其性质研究

从氨基酞菁出发，合成它们的衍生物——四邻苯二甲酰亚胺基金属(Cu^Ⅱ和Co^Ⅱ)酞菁，并对相关化合物进行了质谱、紫外可见光谱、红外光谱表征．其紫外可见光谱中Q带有分裂现象．实现了以氨基酞菁为前体物质进行衍生化的合成实验，讨论了取代基的大小、结构、取代位置及酞菁环中心金属的差异对其Q带分裂现象的影响。     

α-含氧取代酞菁的聚集性质研究

以3-硝基邻苯二腈为原料分别与苯酚和甲醇反应合成3-苯氧基邻苯二腈和3-甲氧基邻苯二腈, 这些α-取代的邻苯二腈以二甲氨基乙醇为溶剂, 在有无醋酸锌条件下环合, 分别形成α-四苯氧基锌酞菁、α-四苯氧基无金属酞菁、α-四甲氧基锌酞菁、α-四甲氧基无金属酞菁, 对产物结构进行了表征. 光谱分析结果表明, 此类锌酞菁在氯仿等非配位溶剂中能自发形成J型聚集体, 其Q带出现一个红移吸收带, 经UV-Vis光谱、荧光光谱及MALDI-TOF质谱分析表明, 该聚集体的形成机理为基于酞菁分子间的锌-氧自配位相互作用.     

对α-四芳氧基取代酞菁溴化位置的思考

为了研究α-四芳氧基取代酞菁在溴化反应中溴原子的取代位置问题,本文合成了1,8,15,22-四(4-甲基苯氧基)酞菁钯(Pc～1)、1,8,15,22-四(2,6-二溴-4-甲基苯氧基)酞菁钯(Pc～2)、1,8,15,22-四(2,4-二特丁基苯氧基)酞菁钯(Pc～3)和1,8,15,22-四(2,4-二特丁基苯氧基)酞菁铜(Pc～4),并对它们分别进行了相同条件下的溴化,得到相应的溴化产物Pc～5、Pc～6、Pc～7和Pc～8.综合对比研究酞菁Pc～1-4及其溴化产物Pc～5-8的最大吸收波长,推测酞菁溴化反应发生在酞菁大共轭体系的苯环上,而不是芳氧取代基的苯环上,并从电子结构的角度简要的说明了原因.     

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.     

磺化2,3-萘酞菁锌(Ⅱ)、钴(Ⅱ)的电子吸收光谱和荧光光谱的研究

研究了磺化2，3-萘酞菁锌(Ⅱ)、钴(Ⅱ)在DMF(N，N-二甲基甲酰胺)、DMSO(二甲基亚砜)、乙醇、水等溶剂中的电子吸收光谱和荧光光谱．萘酞菁配合物的Q带与相应的酞菁配合物Q带相比，电子吸收光谱红移80～90nm，荧光光谱红移约100nm，荧光强度也显增加．在金属萘酞菁中引入磺酸基，配合物的电子吸收光谱Q带发生红移，但是影响不大、对于相同中心金属的配合物，改变溶剂的种类对配合物的电子吸收光谱的Q带影响较大．在金属萘酞菁环上引入一个磺酸基时，在相同溶剂中与无取代萘酞菁相比发生荧光光谱Q带红移，荧光强度增大．但在萘酞菁环上继续引入磺酸基时，荧光强度反而减少．磺化萘酞菁钴比磺化萘酞菁锌有较大的荧光强度．不同浓度下的电子吸收光谱和荧光光谱说明金属萘酞菁有集聚倾向、能形成基激缔合物．     

无金属四噻吩[2,3-b]四氮杂卟啉及其镁配合物的结构和性质的密度泛函理论研究

酞菁(phthalocyanine)及其金属配合物是一类性能良好的多功能材料,在许多领域都有着重要的应用潜力.由于酞菁母体大环:四氮杂卟啉(porphyrazine)及其金属配合物具有紧稠的大环结构和可离域化的共轭π-电子体系,因而近年来人们开始对酞菁外侧的苯环进行各种化学修饰来调节此类物质的物理化学性质.本文工作主要集中于研究给电子噻吩杂环取代酞菁外侧苯环后产生的影响,为今后的实验和理论研究提供依据.本文利用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)中的B3LYP方法,在6-31G(d)基组水平上,对无金属四噻吩[2,3-b]四氮杂卟啉(TTPPzH2)及其镁配合物(TTPPzMg)的结构和性质进行了研究.在本文中,将无金属四噻吩[2,3-b]四氮杂卟啉(TTPPzH2)及其镁配合物(TTPPzMg)分别与无金属酞菁(H2Pc)及其镁配合物(MgPc),无金属卟啉(H2Pz)及其镁配合物(MgPz)在几何结构、原子电荷、分子轨道、紫外可见光谱(UV-Vis)及红外光谱(IR)等方面进行了比较,并且讨论了具有给电子能力的噻吩杂环的取代效应.结果表明:与H2Pz和H2Pc及其相应的金属配合物MgPz和MgPc相比较,由于给电子噻吩杂环的取代降低了体系的对称性,使得相应的键长键角发生了改变,从而影响了相应的键强以及中心NH键的酸性,并且通过比较键长和键角变化的程度解释了引起中心空穴收缩的原因:主要是由于键角的变化对中心空穴的收缩做出了贡献;同时,噻吩杂环的取代对各原子的电荷分布产生了一定的影响,其中对与硫(S)原子相毗邻的Cβ原子的影响最大;与H2Pz和MgPz比较,给电子噻吩杂环的连接增加了体系的共轭程度,减小了最高占据轨道(HOMO)-最低空轨道(LUMO)的能隙,而与H2Pc和MgPc相比较,由于给电子噻吩杂环取代酞菁外侧苯环降低了体系的共轭程度,增大了HOMO-LUMO的能隙,使得TTPPzH2和TTPPzMg的Q吸收带(酞菁类化合物的特征吸收峰)向长波方向移动发生了蓝移.其中,需要强调的是,由于低占据轨道的较大的离域性使得TTPPzH2和TTPPzMg的B带(酞菁类化合物的特征吸收峰)发生了红移;通过对轨道能量、分子轨道对称性及HOMO和LUMO轨道图进行比较,说明由于噻吩杂环中硫原子的贡献降低了各分子轨道的能级,同时改变了各分子轨道的对称性;此外,通过分析紫外可见光谱,发现与H2Pc和MgPc相类似,TTPPzH2和TTPPzMg在300～400nm处出现了两个明显的B吸收带,在500～600nm处出现了两个明显的Q吸收带,与四氮杂卟啉类化合物的Q吸收带范围(535～617nm)相一致;借助于正则坐标分析,对红外光谱中的重要吸收峰和振动模式进行了指认和分析.由于给电子噻吩杂环的取代使得计算和模拟的IR光谱发生了蓝移,但是大体的变化趋势与相关的理论和实验研究结果相一致,进一步说明了我们所选择的研究方法的合理性.此外,本文工作对于今后研究酞菁类化合物的结构和光谱性质具有深远的意义.     

锌酞菁类染料的氧化还原电位研究

金属酞菁染料对红光及近红外光有强吸收,并且具有半导体的性能。由于它具有性质稳定,合成方便等特点,这类染料在传统的染料、颜料工业中有着重要的地位;近年来在太阳能的利用,氧化还原反应的光敏化等方面引起了人们很大的注意。由于一般的金属酞菁染料的溶解度很差,常使它们的应用受到限制。为此,我们合成了一系列在环上带有各种取代基的锌酞菁染料(ZnPcR),以改善其溶解度,并对它们的氧化还原电位和分子结构与轨道能级之间的关系进行了研究。     

四溴-2,3-萘酞菁铅的合成及性质研究

以1,8-二氮杂双环[5.4.0]+-碳烯-7(DBU)为催化剂合成了中心原子为重原子铅、环取代基为重原子溴的萘酞菁配合物四溴-2,3-萘酞菁铅[PbNcBr₄],并研究了该配合物的电子吸收光谱、热稳定性、光限幅特性及重原子对其光限幅特性的影响及其机理.该配合物在近红外区(795～825nm)有强吸收(Q带),溴取代可使配合物Q带略微蓝移,溶剂的极性对配合物的电子吸收光谱有较大影响.该配合物具有较高的热稳定性,气氛对其热稳定性有明显影响,其在N₂气氛中的热稳定性明显比在O₂气氛中的高;在O₂气氛中为一步分解,在N₂气氛中为多步分解.标题配合物具有优异的非线性光限幅特性,在高线性透射率88%时的限幅阈值为148mJ/cm²,限幅幅值为332mJ/cm²,损伤阈值约为3J/cm²,其光限幅特性明显优于光限幅新材料C₆₀(透射率70%时,限幅阈值大于240mJ/cm²).重原子铅和溴可显著优化材料的非线性光限幅特性.     

近红外激光防护染料

以激光防护和隐身材料为需求背景，概述了菁类染料(含多次甲基菁染料、方酸菁和克酮酸菁染料、薁染料)、酞菁类染料(含普通酞菁和萘酞菁)、金属络合物染料、醌型染料、偶氮染料、游离基型染料、芳甲烷型染料、苝类染料等近红外吸? 杖玖系难芯孔纯黾敖埂? $601$ADuetotherequirementofnear-infraredlaserprotectivedyesandlaserstealthmaterials,thisreviewfocusedontheresearchprogressofnear-infraredabsorbingdyes,andsomesuggestionswereputforwardonthefutureresearch.Someofthemostimportanttechnicalrequiremnetsforlaser-protectivedyeswithintheplasticareasfollows:sharpabsorptionbandsatspecificwavelengthscorrespondingtolaseremission,excellentlightfastness,robustthermalandchemicalstability,stabilitytoambientconditions,highopticaldensityandscotopicluminoustransmission,goodsolubilityinplasticandlowtoxicity.Thisreviewpaidattentiontothepropertiessuchasthemaximumabsorptionwavelengthandtheabsorptionintense,attentionhadbeendirectedtowardseighttypesnear-infrareddyes:cyaninedyeswhichincludedpolymethinedyesandsquaryliumorcroconiumdyes,phthalocyaninesandnaphthalocyanines,metalcomplexdyes,quinonedyes,azodyes,radicaldyes,multiphenylmethanedyesandperylenedyes.Otherkindsofnear-infrareddyeswerealsomentioned,suchasaromaticannulenes,planescontainignso-callednonbenzenoidaromaticrings,cycliccross-conjugatedhydrocarbonshavinginsertedp-quiniodring,fluorenyliumdyeswithinorganicanions,donor-acceptorcyclophanes,tetrapyrazinoporphyrazinesandpentaazadentateexpandedporphyrinsetal.Allofthedyesmentionedabovehadsomegoodpropertiesforuseasthenear-infraredlaserprotectivedyesandlaserstealthmaterials,buttherealsoexisteddefectsineverykindofdyes.     

Molecular engineering of sensitizers for dye‐sensitized solar cell applications

Dye‐sensitized solar cells (DSSCs) have attracted considerable attention in recent years as they offer the possibility of low‐cost conversion of photovoltaic energy. This account focuses on recent advances in molecular design and technological aspects of sensitizers based on metal complexes, metal‐free organics and tetrapyrrolic compounds which include porphyrins, phthalocyanines as well as corroles. Special attention has been paid to the design principles of these dyes, and co‐sensitization, an emerging technique to extend the absorption range, is also discussed as a way to improve the performance of the device. This account also focuses on recent advances of efficient ruthenium sensitizers as well as other metal complexes and their applications in DSSCs. Recent developments in the area of metal‐free organic and tetrapyrrolic sensitizers are also discussed. DOI 10.1002/tcr.201100044     

Effect of metal ions on the determination of polymer flocculants using triphenylmethane dyes

Transition and heavy metals interfere with the spectrophotometric determination of flocculants based on the formation of their ion associates with triphenylmethane dyes (TPM). The absorption band of metal complexes with these reagents overlaps the absorption band of the associates; moreover, metal ions enhance the absorption of the associate. The increase in sensitivity is accompanied by a decrease in repeatability; therefore, the detection limits of flocculants change insignificantly. In the determination of flocculants in water at a level of 1 mg/L and above, these metals should be separated or masked in advance.     

Photochemical studies of tetra-2,3-pyridinoporphyrazines

Tetra-2,3-pyridinoporphyrazines and the corresponding water-soluble N,N′,N′′,N′′′-tetramethyl-tetra-2,3-pyridinoporphyrazine complexes, containing central metal atoms; M=Ge, Sn, Si and Zn, were synthesized and their photochemical properties were investigated. The reductive quenching of pyridinoporphyrazines excited states, enhanced relative to phthalocyanines, was considered as the first photochemical step of dyes phototransformation in dimethylformamide (DMF) and dimethylsulfoxide (DMSO) solutions under irradiation with visible light. Efficiency of singlet oxygen photosensitization decreases significantly in the row phthalocyanines, unquaternized, quaternized tetra-2,3-pyridinoporphyrazine metallocomplexes.     

Bis(2-pyridyl)-substituted boratriazaindacene as an NIR-emitting chemosensor for Hg(II)

Aryl-substituted boratriazaindacenes (Aza-Bodipy's) are a new class of dyes with long wavelength absorption and emissions. We now report the first application of these dyes in metal ion sensing. 2-Pyridyl substituents at positions 1 and 7 create a well-defined pocket for metal ion binding. The chemosensor described here is selective for Hg(II) ions, and both absorption and emission spectra display large changes that would allow ratiometric sensing. [reaction: see text].     

Synthesis and Characterization of New Unsymmetrically Substituted Phthalocyanines

 Unsymmetric metallophthalocyanines (M=Zn, Co, Ni) carrying alkylthio and acetyloxyethylthio groups on peripheral positions were prepared from 4,5-bis-alkylthio-phthalonitrile, 4,5-bis-(acetyloxyethylthio)-phthalonitrile, and the corresponding anhydrous metal salts Zn(CH₃COO)₂, NiCl₂, and CoCl₂. The extremely soluble compounds were characterized by their IR, ¹H NMR, and UV/Vis spectra. Their long wavelength absorption band was found to be bathochromically shifted; their solubility is superior to that of symmetrical phthalocyanines.     

Phthalocyanine conjugates with carbohydrates: synthesis and aggregation in aqueous solutions

The review is focused on the current state of the synthesis of glycosylated phthalocyanines and their precursors, mono-, di-, and tetraglycosyl phthalonitriles. Features of the synthesis of phthalogen conjugates with carbohydrates and the formation of related metal phthalocyanine complexes are discussed. The formation of aggregates of phthalocyanines in various media exerts a significant effect on the physicochemical and photochemical properties of phthalocyanine macrocycles, which is especially important in the practical use of phthalocyanines as photosensitizes. An aggregation of phthalocyanine conjugates in aqueous solutions strongly decreases the quantum yield of singlet oxygen, thus diminishing the biological activity of these compounds. Specific features of phthalocyanine conjugate aggregation with carbohydrates in aqueous solutions, organic solvents, and some their mixtures are analyzed.     

Spectroscopic and thermal properties of short wavelength metal (II) complexes containing alpha-isoxazolylazo-beta-diketones as co-ligands

Two new azo dyes of alpha-isoxazolylazo-beta-diketones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni2+ and Cu2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability.     

Glycosylated zinc(II) phthalocyanines as efficient photosensitisers for photodynamic therapy. Synthesis, photophysical properties and in vitro photodynamic activity

Treatment of 3- or 4-nitrophthalonitrile with 1,2:5,6-di-O-isopropylidene-alpha-d-glucofuranose or 1,2:3,4-di-O-isopropylidene-alpha-d-galactopyranose in the presence of K(2)CO(3) gave the corresponding glycosubstituted phthalonitriles. These precursors underwent self-cyclisation, or mixed-cyclisation with the unsubstituted phthalonitrile, to afford the tetra- or mono-glycosylated zinc(ii) phthalocyanines, respectively. As shown by absorption spectroscopy, these compounds were not significantly aggregated in organic solvents, giving a weak to moderate fluorescence emission. Upon irradiation these compounds could sensitise the formation of singlet oxygen in DMF, with quantum yields in the range of 0.40-0.66. The in vitro photodynamic activities of these compounds against HepG2 human hepatocarcinoma and HT29 human colon adenocarcinoma cells were also studied. The mono-glycosylated phthalocyanines exhibited significantly higher photocytotoxicity compared with the tetra-alpha-glycosylated analogues, having IC(50) values down to 0.9 muM. The tetra-beta-glycosylated counterparts were essentially inactive. The lower photocytotoxicities of the tetra-glycosylated phthalocyanines are in line with their lower cellular uptake and/or higher aggregation tendency as reflected by weaker intracellular fluorescence, and lower efficiency at generating intracellular reactive oxygen species. For the mono-glycosylated phthalocyanines, the higher uptake can be attributed to their hydrophilic saccharide units, which increase the amphiphilicity of the macrocycles.