Stacking Control by Molecular Symmetry of Sterically Protected Phthalocyanines

The synthesis and characterization of two phthalocyanine (Pc) structural isomers, 1 and 2, in which four 2,6-di(hexyloxy)phenyl units were attached directly to the 1,8,15,22- or 1,4,15,18-positions of the Pc rings, are described. Both Pcs 1 and 2 exhibited low melting points, i.e., 120 and 130 °C respectively, due to the reduction in intermolecular π-π interaction among the Pc rings caused by the steric hindrance of 2,6-dihexyloxybenzene units. The thermal behaviors were investigated with temperature-controlled polarizing optical microscopy, differential scanning calorimetry, powder X-ray diffraction, and absorption spectral analyses. Pc 1, having C_4h molecular symmetry, organized into a lamellar structure containing lateral assemblies of Pc rings. In contrast, the other Pc 2 revealed the formation of metastable crystalline phases, including disordered stacks of Pcs due to rapid cooling from a melted liquid.     

四羧基铜酞菁共振散射法测定硫酸庆大霉素

在弱酸性条件下,四羧基铜酞菁(CuC4Pc)与硫酸庆大霉素(GEN)反应形成离子缔合物,使体系的共振散射强度增大,据此建立了以四羧基铜酞菁为探针测定GEN的新方法.在λ为362 nm处,共振散射强度(△IRLS)最大且△IRLS与GEN的浓度在0.05～1.50μg/mL范围内成正比,检出限为0.044μg/mL.将方法用于硫酸庆大霉素注射液的测定,结果满意。     

醋酸溶液中Pd-CuPc/Y催化甲烷选择氧化制甲醇

以氯化铜、钼酸铵、苯酐、氯化铵、尿素和NaY分子筛为原料,采用苯酐-尿素法制备了酞菁铜/分子筛复合物CuPc/Y.采用等体积浸渍法将金属钯担载在CuPc/Y上制备了Pd-CuPc/Y催化剂,并在醋酸水溶液中考察了其催化甲烷选择氧化合成甲醇反应的性能,结果表明,催化性能与反应温度、溶剂中CH₃COOH与H₂O的混合比例、对苯醌用量、反应时间等因素有关,在0.5%Pd-0.5%CuPc/Y添加量0.5 g、CH₃COOH与H₂O体积比4∶1、对苯醌用量1 000 μmol、反应时间3 h、反应温度150 ℃的条件下,甲醇的最佳生成量为1 840 μmol.Pd-CuPc/Y催化剂可以多次循环使用,但由于催化剂流失和催化剂表面的钯粒子聚集的原因,循环使用后的催化剂催化活性有所下降.Pd-CuPc/Y在醋酸溶液中催化甲烷选择氧化合成甲醇是亲电取代反应和活性氧物种氧化共同作用的结果.     

New polythiophenes bearing electron-acceptor phthalocyanine chromophores

Two new donor-acceptor copolymers comprising a polythiophene backbone, and bearing phthalocyanine chromophores on the side chains have been prepared. Preliminary photophysical characterization of these materials by FTIR photoinduced absorption indicates that electron transfer from the polythiophene to the phthalocyanine units takes place.     

硅胶键联MPc的制备及其在氧活化中的作用

过渡金属酞等配合物（MPC）用手均相液相氧化中作催化剂已有不少报导，象许多均相催化剂一样，MPC用于均相反应存在着难于从反应体系中分离出来的问题．把均相配合物催化剂固载在无机氧化物如硅股或有机高分子载体上是解决这一问题的一种方法．我们曾尝试把MP。固载在分子筛载体和硅胶载体上，并用ESR研究其对O2的活化作用[1，2]．本文报导MPc通过共价键键联固载在SiO2上，并研究其对O2的活化作用．1实验部分1．1试剂HSIC13为日本东京化成株式会社产品，二级试剂·发烟硫酸（SO。质量分数大于20％）为分析纯试剂．PCl5为化学纯试…     

一种新型酞菁类光蚀刻记录材料的光生酸性质研究

通过研究对甲苯磺酸酯空心酞菁的性质,发现该化合物在紫外光照射下可生酸,是一种光生酸剂.由于酞菁类化合物本身具有光催化氧化反应的性能,因此这类光生酸剂在光蚀刻技术中将有很好的应用潜能.     

Synthesis,Photophysical and Electrochemical Properties of Amide‐Linked Phthalocyanine‐Fullerene Dyad

A new amide‐linked phthalocyanine‐fullerene dyad ZnPc‐C₆₀ was synthesized and characterized. The photophysical and electrochemical properties of the ZnPc‐C₆₀ dyad were investigated. The fluorescence spectrum and quantum yield in different solvents showed the occurrence of photoinduced electron transfer (PET) from the singlet excited ZnPc to C₆₀, which was further confirmed by nanosecond transient absorption spectra and cyclic voltammetry data. The free energy change for charge separation (ΔG_CS) was estimated to be exothermic with ?0.51 eV, which favored the formation of charge‐separation state. The PET from ZnPc to C₆₀ in ZnPc‐C₆₀ made the dyad exhibit stronger reverse saturable absorption performance compared with C₆₀ and the control sample in the Z‐scan experiments, which indicated the synergistic effect of two active moieties in the dyad.     

新型可溶性空心酞菁磺酰类化合物的合成及性质研究

以空心酞菁(H2Pc)为原料,采用取代基转化法,经过氯磺酰化和酯化合成了空心酞菁磺酰氯和空心酞菁磺酸对甲氧基苯酯,经元素分析,1H NMR,IR,UV-Vis等方法,确定了空心酞菁磺酰氯和空心酞菁磺酸对甲氧基苯酯的组成分别为H2Pc(SO2Cl)4和H2Pc(SO2-p-OC6H4OCH3)4.结果表明,此两种产物在空心酞菁的苯环上引入取代基后,长波吸收增强,溶解度高,热稳定性良好.     

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.     

Mechanism of singlet-oxygen induced delayed fluorescence of bacteriopheophytin in laser excitation

The relative intensity of photosensitized phosphorescence of singlet oxygen (¹O₂) at 1270 nm (L₁₂₇₀) and¹O₂-induced delayed fluorescence (L_df) of bacteriopheophytin a (BPh) (770 nm) in air-saturated solutions of BPh in hexafluorobenzene in excitation by 337-nm pulses of a nitrogen laso is investigated. It is established that L_df≪L₁₂₇₀. The ratio of the initial intensity of delayed fluorescence and phosphorescence of¹O₂(L_df)₀/(L₁₂₇₀)₀ changed from 0.02 to 0.30 as a function of the energies of laser pulses (2.5–5.0 mJ/cm¹) and the BPh concentration (6–18 μM). As the index of quantum efficiency of the delayed fluorescence, the authors used the coefficient