可溶性氧钒酞菁的非共振三阶非线性光学性质

合成了不同取代基和不同取代基位置的可溶性氧钒酞菁化合物, 并采用简并四波混频方法测定了这些化合物在非共振条件下的<γ>值和X^(^3^)值, 它们分别在10^-^3^1esu及10^-^1^0~10^-^9esu数量级。酞菁环上取代基的性质将影响化合物的<γ>值, 取代基的给电子能力越强, <γ>值就越大, 而取代基位置对<γ>值的影响较小。     

可溶性氧钒酞菁的非共振三阶非线性光学性质

合成了不同取代基和不同取代基位置的可溶性氧钒酞菁化合物,并采用简并四波混频方法测定了这些化合物在非共振条件下的<γ>值和 x~((3)) 值,它们分别在10~(-31)esu及10~(-10)～10~(-9)esu数量级、酞菁环上取代基的性质将影响化合物的<γ>值,取代基的给电子能力越强,<γ>值就越大,而取代基位置对<γ>值的影响较小.     

烷氧基取代金属酞菁的合成及其吸收光谱性质

合成了６种烷氧基取代的酞菁化合物，并进行了元素分析．研究了它们在溶液和薄膜中的吸收光谱性质．     

以二苯甲酮为端基的第一代树状取代酞菁锌的合成

4-甲基二苯甲酮经N-溴代丁二酰亚胺溴代制得4-溴甲基二苯甲酮(1);1与3,5-二羟基苯甲醇反应合成了外围带有二苯甲酮取代基的第一代树枝状分子3,5-二(二苯甲酮-4-甲氧基)苯甲醇(2);2与4-硝基邻苯二甲腈缩合制得外围带有二苯甲酮取代基的第一代树枝状分子4-[3,5-二(二苯甲酮-4-甲氧基)苯甲氧基]邻苯二甲腈(3);3经"液相法"环合生成外围带有二苯甲酮取代基的第一代树枝状分子取代的酞菁锌配合物——四[3,5-二(二苯甲酮-4-甲氧基)苯甲氧基]锌酞菁[ZnPc(C35H27O5)4],其结构经UV,1HNMR,IR和MS表征。     

相转移催化合成酯基取代酞菁铜及其光导性能

酞菁配合物的大π键共轭体系使其具有独特的物理化学性能．但酞菁的难溶性,限制了其进一步的研究和应用．Baker等首次制备了可溶性酞菁单分子膜,并将其应用到光电池中;随后,已有大量的相关研究报道．作为常见的可溶性酞菁衍生物,酯基取代酞菁由于含酯基的前体物质高温分解而不能采用直接缩合的方法,     

新型可溶性酞菁的合成和光致发光及电致发光性质

以3(4)-硝基邻苯二腈和对甲氧基苯酚为原料, 经过两步反应合成了α(β)-四(4-甲氧基苯氧基)酞菁锌, 通过谱学方法和元素分析表征了其结构. 比较研究其溶液和旋涂膜的紫外可见光谱、光致发光光谱和固体薄片的光致发光光谱. 并以其旋涂膜为发光层制备了电致发光器件, 研究其电致发光性质. 结果表明, 固态酞菁材料与其溶液的荧光发射波长相比均向长波方向移动了145 nm以上, 而且都有不同程度的宽展. 在固态下β-位取代酞菁荧光发射波长红移的程度比α-位取代酞菁大. 电致发光光谱的发射波长和其旋涂膜的光致发光光谱的发射波长基本一致, 大约在856和862 nm左右. 在固态下酞菁分子排列紧密, 分子间相互作用增强导致了荧光发射波长的巨大红移.     

可溶性亚酞菁的合成,光谱及聚集性质的研究

酞菁类化合物作为一类有机功能材料,如导体或半导体、气敏元件、电化学催化剂、电致变色及光致变色材料、光动力疗法的药物以及非线性光学材料等^[1],已经受到化学家和材料学家们的关注.近几十年来,化学家们已经成功地合成出了带各种不同取代基和含有不同中心金属原子的酞菁或萘酞菁类化合物,并对它们的物化性质进行了广泛而深入的研究.     

钒氧酞菁薄膜瞬态光电压性能的研究

本文分别用1064nm, 532nm和 355nm激发波长的YAG脉冲激光对所制备的phase Ⅱ结构钒氧酞菁膜Al\phase ⅡVOPc\ITO夹心电池进行瞬态光电压响应研究.随着3种波长激发光脉冲强度的增加, 瞬态光电压信号均增强. 激发光波长1064nm、532nm处于酞菁膜Q-带吸收区肩部, 光电压的极性与激发光入射方向无关, 均为负信号; 而激发光波长 355nm处于酞菁膜B-带, 光电压的极性与激发光入射方向有关, 从ITO极方向激发产生正电压信号, 从A1极激发产生负电压信号. 激发光波长对夹心电池的光电压产生有明显的作用, 光电压产生过程中应存在不同的机理. 这与前文^[1]对同一夹心电池稳态光电压响应研究所推断的结论一致.     

钒氧酞菁的合成及其薄膜结构与光电性能的研究

自从60年前^[1]金属酞菁被发现以来,就引起人们的广泛兴趣,其原因主要在于它们在染料颜料、光化学、催化、和成像中的应用. 和许多其它酞菁衍生物一样,钒氧酞菁具有光导和半导体特性,这使得它在光电子学、电子成像、化学传感器、甚至于微电子器件中有潜在的十分光明的应用前景^[2]. 例如, 钒氧酞菁在电子成像体系中已成为有用的感光材料. 近年来,金属酞菁等有机材料的结晶薄膜开始不断地吸引人们的注意力. 人们考察了不同的金属酞菁如: 酞菁铜、酞菁铅、酞菁镍、和酞菁锡 等的光电导和光电压^[3]. 通常酞菁以几种不同的多晶异构体、即以不同的晶体排列结构方式存在. 因此,其光电特性不仅取决于分子中心的金属原子、而且取决于它们的晶体结构. 总之,值得我们研究钒氧酞菁薄膜的光电特性以及它与吸收光谱和薄膜晶体结构的关系.     

芳氧基取代酞菁锌的合成及光物理化学性质

合成得到3-(5-氨基-萘氧基)邻苯二甲腈(C18H11N3O)、4-(5-氨基-萘氧基)邻苯二甲腈(C18H11N3O)、3-联苯氧基邻苯二甲腈(C20H12N2O)及4-联苯氧基邻苯二甲腈(C20H12N2O)4种未见报导的取代邻苯二甲腈,以此为前躯体合成了四[α-(5-氨基-萘氧基)]酞菁锌(C72H44N12O4Zn)、四[β-(5-氨基-萘氧基)]酞菁锌(C72H44N12O4Zn)、四[α-(联苯氧基)]酞菁锌(C80H48N8O4Zn)和四[β-(联苯氧基)]酞菁锌(C80H48N8O4Zn)4种未见报导的芳氧基取代酞菁锌配合物。通过测定它们的紫外-可见吸收光谱、荧光发射光谱,获得其最大吸收波长及其摩尔消光系数、最大发射波长、荧光量子产率(ΦF)、单线态氧量子产率(ΦΔ)及光降解速率常数并与其类似物进行了比较,探讨了它们的光物理光化学性质的构效关系。研究结果表明四[α-(联苯氧基)]酞菁锌在红光区具有大的摩尔消光系数,且具有较高的ΦΔ,有望开发成为光动力治疗用光敏剂。     

Optical-limiting and photophysical properties of two soluble chloroindium phthalocyanines with alpha- and beta-alkoxyl substituents.

Two soluble heavy-metal phthalocyanine derivatives, namely, tetra-alpha-(2-ethylbutoxy) chloroindium phthalocyanine (alpha-InPcCl) and tetra-beta-(2-ethylbutoxy) chloroindium phthalocyanine (beta-InPcCl), were synthesized. Their optical-limiting properties in THF solution were investigated with a 532 nm nanosecond laser. The differences in the optical-limiting properties are attributed to their different photophysical properties. alpha-InPcCl is superior to beta-InPcCl as optical-limiting material, alpha substitution could be a useful factor to be considered in designing optical limiting materials based on metal phthalocyanines.     

2,9,16,23-四联苯基金属酞菁的合成、溶解性及光学性质

合成了2,9,16,23-四联苯基金属(Fe,Co,Ni,Cu和Zn)酞菁。研究了合成产物的质谱、溶解性、紫外光谱以及荧光光谱．结果表明,取代基使金属酞菁的溶解性增加,不发生二聚,紫外光谱发生红移。     

Aggregation of water soluble octaanionic phthalocyanines and their photoinactivation antimicrobial effect in vitro

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Thiochalcone substituted phthalocyanines for dye-sensitized solar cells: Relation of optical and electrochemical properties for cell performance

The new peripherally tetra-substituted metallophthalocyanines (MPcs, M=Zn, Co, Ni) bearing the chalcone, (E)-3-(4-hydroxyphenyl)-1-(thiophen-2-yl)prop-2-en-1-one, for dye-sensitized solar cells (DSSCs) were synthesized. FT-IR, ¹H NMR, ¹³C NMR, and UV–Vis spectroscopy techniques were utilized for characterization of all the MPcs. Electrochemical, optical and photovoltaic properties of all the MPcs as sensitizers were examined. Electrochemical studies reveal that while the ZnPc (4) and NiPc (6) give only Pc ring-based redox reactions, the CoPc (5) shows redox reactions based on both the central metal and the ring due to the metal 3d orbitals lying between the Pc HOMO and LUMO. The DSSC based on 5 gave the lowest power conversion efficiency (0.51%), perhaps due to the presence of a redox active central metal ion in the core of the complex, which results in a decrease electron transfer in the device. However, cells based on the other complexes including redox inactive central metal ions, which cannot reduce electron transfer, showed reasonable power conversion efficiencies of 1.27% and 1.11% for 4 and 6, respectively. The slight difference between the efficiencies can be attributed to higher molar extinction coefficient and narrower band gap of 4 than 6, which ensure a higher photocurrent and broader light absorption in the visible region.     

Photophysical characterization of dysprosium, erbium and lutetium phthalocyanines tetrasubstituted with phenoxy groups at non-peripheral positions

Dysprosium bis-phthalocyanine and monomeric phthalocyanines of erbium and lutetium with non-peripheral phenoxy substituents have been synthesized using two different preparative routes. Photophysical studies on these phthalocyanines revealed that the triplet states of dysprosium and erbium are not populated while the monomeric phthalocyanine complex of lutetium is populated with a quantum yield of 0.83 and a lifetime of 25 μs in DMSO. It was further found that the phthalocyanine complex of lutetium was capable of photochemical generation of singlet state molecular oxygen with yield of 0.71 in THF, thus a promising photosensitizer. However, the three phthalocyanine molecules have very low fluorescence quantum yields of less than 0.01.     

Effect of axial ligands on the photophysical properties of new silicon(IV) phthalocyanines

A series of axial di-substituted silicon(IV) phthalocyanines with electron-donating and electron-withdrawing properties were synthesized. The compounds were characterized by elemental analysis, ¹H NMR, IR, and ESI-MS. The effect of axial ligands on the photophysical properties of silicon phthalocyanines was studied by UV/Vis, steady-state and time-resolved fluorescence spectroscopic analyses. Compared with silicon phthalocyanines with electron-donating properties, silicon phthalocyanines with electron-withdrawing properties could expand the π-conjugation in the dyes, resulting in a redshift of Q bands, lower fluorescence emission intensity and fluorescence quantum yields, but increasing fluorescence lifetimes. These results strongly suggest that the molecular design of phthalocyanines is essential for construction of photoactive materials.     

Syntheses and properties of octa-, tetra-, and di-hydroxy-substituted phthalocyanines

The synthesis and photophysical properties of a new series of zinc(II) phthalocyanines (ZnPcs) bearing multiple hydroxy and tert-butyl groups are reported. The X-ray structures of two phthalonitriles and one ZnPc are presented. All hydroxy-substituted ZnPcs show low fluorescence quantum yields in DMSO and complete fluorescence quenching in aqueous solutions, but high singlet oxygen quantum yields in DMSO (0.2-0.7). Our results suggest that the tetra- and octa-hydroxy ZnPcs might find application as photosensitizers in the PDT treatment of cancer.