取代席夫碱铜金属卟啉的微波辅助合成

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秦燕芳, 齐勇, 黄月君, 侯英杰, 安宇, 张登科, 韩云科, 潘继刚. 取代席夫碱铜金属卟啉的微波辅助合成. 应用化学, 32(1): 53-59
QIN Yanfang, QI Yong, HUANG Yuejun, HOU Yingjie, AN Yu, ZHANG Dengke, HAN Yunke, PAN Jigang. Microwave-assisted Synthesis of Cu(Ⅱ)meso-Tetra (Schiff-base substituted phenyl)porphyrins. Chinese Journal of Applied Chemistry, 32(1): 53-59 复制到剪切板

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取代席夫碱铜金属卟啉的微波辅助合成

秦燕芳^a, 齐勇^a, 黄月君^b, 侯英杰^a, 安宇^a, 张登科^a, 韩云科^a, 潘继刚^a,^*

^a山西大学化学化工学院太原 030006

^b药科职业学院太原 030031

通讯联系人:潘继刚,副教授; Tel:0351-7010588; E-mail:panjigang_sxu@126.com; 研究方向: 有机化学

收稿日期:2014-08-14

摘要

微波辅助合成了取代席夫碱铜金属卟啉。实验结果表明,取代苯甲醛与四(对氨基苯基)铜金属卟啉的缩合反应速率和产率与芳香醛取代基的种类有关,含吸电子基团的芳香醛大于含给电子基团的芳香醛,且随吸电子性的增强而增加,随给电子性的增强而减少。水杨醛席夫碱铜金属卟啉侧链可与铜离子在碱性条件下形成铜配合物,其催化氧化环己烷的转化率达到了7.68%,环己酮的选择性达到了60.87%。

关键词: 四(对氨基苯基)铜卟啉; 取代席夫碱铜金属卟啉; 微波; 铜配合物; 催化氧化

中图分类号:O641.4;O622.6 文献标志码:A 文章编号:1000-0518(2015)01-0053-07

Microwave-assisted Synthesis of Cu(Ⅱ)meso-Tetra (Schiff-base substituted phenyl)porphyrins

QIN Yanfang^a, QI Yong^a, HUANG Yuejun^b, HOU Yingjie^a, AN Yu^a, ZHANG Dengke^a, HAN Yunke^a, PAN Jigang^a,^*

^aSchool of Chemistry and Chemical Engineering,Shanxi University,Taiyuan 030006,China

^bShanxi Pharmaceutical College,Taiyuan 030031,China

Corresponding author:PAN Jigang, associate professor; Tel:0351-7010588; E-mail: panjigang_sxu@126.com; Research interests:organic synthesis

Abstract

Cu(Ⅱ) meso-tetra(Schiff-base substituted phenyl)porphyrins were synthesized under microwave heating. The experimental results show that the species of substituents on substituted benzaldehyde affect the condensation reaction rates and yields between benzaldehyde and Cu(Ⅱ) meso-5,10,15,20-tetrakis(4-aminophenyl)porphyrin. Cu complex can be formed between the side-chain of salicylaldehyde-Schiff base copper metalloporphyrin and copper ions in alkaline conditions. The conversion and the selectivity of its catalytic oxidation of cyclohexane to cyclohexanone is up to 7.68% and 60.87%, respevtively.

Keyword: Cu(Ⅱ)meso-tetrakis(aminophenyl)porphyrin; Cu(Ⅱ)meso-tetra(Schiff-base substituted phenyl) porphyrins; microwave; Cu complex; catalytic oxidation

Show Figures

具备优异光电效应^[1]、特定生物功能^[2]、良好理化性能^[3]的有机大分子卟啉类化合物被广泛应用于生物科学、医药科学、材料科学、催化科学等领域^{[4, 5, 6, 7]}。人们不断研究新型功能型卟啉并将其应用于切割DNA、太阳能电池、工业催化剂甚至动物饲料上^{[8, 9, 10, 11]}。席夫碱及其金属配合物被视为一种高效催化剂, 大大提高了烯烃催化环氧化产率^{[12, 13]}, 同时席夫碱还被视为一类高活性抑菌剂^{[14, 15, 16]}。席夫碱-卟啉类化合物作为一类链接卟啉与席夫碱优良性能的功能大分子化合物, 具有广阔的研究价值与应用价值。近年来, 席夫碱卟啉类化合物得到了广泛关注^{[18, 19]}, 在工业催化^[20]、分析科学^[21]以及功能大分子^{[22, 23]}等领域应用广泛, 研究席夫碱金属卟啉的合成与性质意义重大。

本文以对硝基苯甲醛为原料微波合成了四(对硝基苯基)卟啉, 经氯化亚锡还原得到四(对氨基苯基)卟啉并制备了其铜金属卟啉。并利用微波辅助合成了取代席夫碱铜金属卟啉, 研究了取代基对席夫碱-金属卟啉合成产率的影响并优化了合成路线, 利用紫外-可见光分光光度法研究了水杨醛席夫碱铜金属卟啉在碱性条件下与铜离子的配合过程。制备了水杨醛席夫碱铜金属卟啉-铜配合物, 研究了其对环己烷的催化氧化反应。

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	图1 取代席夫碱铜金属卟啉的合成路线Fig.1 Preparations of Cu(Ⅱ )meso-tetra(schiff-base substituted phenyl)porphyrins

1 实验部分

1.1 仪器和试剂

DRX300MHz型超导核磁共振仪(CDCl₃、DMSO-d₆为溶剂, TMS为内标, 瑞士Bruker公司); GC6890型气相色谱仪(美国Agilent公司); Vario型元素分析仪(德国Elementar公司); UV-2450型紫外可见分光光度计(日本Shimadzu公司); RE-501型旋转蒸发仪(郑州合众仪器有限公司); ZF-20D型暗箱式紫外分析仪(巩义市予华仪器有限责任公司); Baker-flex型薄层色谱板(德国Merck公司); FAB-MS型质谱仪(美国Venigen公司)。实验所用试剂均为分析纯。

1.2 合成

1.2.1 Meso-5, 10, 15, 20-四(对硝基苯基)卟啉的合成方法一:将15.1 g(0.1 mol)对硝基苯甲醛加入到500 mL反应瓶中, 加入300 mL丙酸, 8 mL乙酸酐, 加热溶解, 加入6.7 g(0.1 mol)吡咯, 回流4 h, 冷却至室温, 抽滤, 甲醇洗涤, 干燥, 将所得的紫黑色固体加入到200 mL吡啶中, 回流30 min, 趁热抽滤, 甲醇洗涤, 将所得的紫色固体用THF煮沸, 加入大量甲醇, 冷却抽滤, 甲醇洗涤。干燥得4.87 g紫色固体(收率24.51%)。

方法二:将1.51 g(0.01 mol)对硝基苯甲醛加入到50 mL反应瓶中, 加入30 mL丙酸, 0.8 mL乙酸酐, 加热溶解, 加入0.67 g(0.01 mol)吡咯, 微波反应20 min。后处理同方法一(收率26.43%)。 mp > 300 ℃, C₄₄H₂₆O₈N₈元素分析值(计算值)/%:C 66.52(66.50), H 3.34(3.30), N 14.04(14.10); UV-Vis(DMF), λ _max/nm(lg ε ):423(5.33), 515(4.10), 551(3.83), 590(3.69), 646(3.53)。

1.2.2 Meso-5, 10, 15, 20-四(对氨基苯基)卟啉的合成将7.95 g(10 mmol)四(对硝基苯基)卟啉加入到1000 mL反应瓶中, 加入250 mL浓盐酸, 搅拌溶解, 加入35 g SnCl₂· 2H₂O, 80 ℃下反应30 min, 冷却后加入250 mL水, 搅拌片刻后抽滤, 滤饼用6 mol/L的盐酸洗涤, 将滤饼热溶于水中, 用NaOH溶液调pH值至7, 再用浓氨水调至8, 抽滤, 水洗, 干燥。用V(乙酸乙酯)∶ V(丙酮)=5∶ 1硅胶柱层析, 收集酒红色部分, 旋干得6.41 g紫色固体(收率94.96%)。 mp > 300 ℃, C₄₄H₃₄N₈元素分析值(计算值)/%:C 78.27(78.32), H 5.11(5.08), N 16.65(16.61); ¹H NMR(300 MHz, DMSO-d₆), δ :-2.76(bs, 2H, NH), 5.53(s, 8H, NH₂), 6.97(d, 8H, m-Ar2H), 7.81(d, 8H, O-Ar2H), 8.87(s, 8H, β CH); UV-Vis(DMF), λ _max/nm(lg ε ):427.5(5.46), 522.5(4.04), 564(4.09), 597(3.56), 656(3.76)。

1.2.3 Meso-5, 10, 15, 20-四(对氨基苯基)铜金属卟啉的合成将6.75 g(10 mmol)四(对氨基苯基)卟啉溶于15 mL DMF中, 加入0.05 mol乙酸铜, 回流反应30 min, 冷却至室温, 加入大量水, 二氯甲烷萃取3次, 有机相干燥后硅胶柱层析, 流动相为二氯甲烷, 收集紫红色部分旋干得7.12 g紫红色晶体(收率96.74%)。 mp > 300 ℃, C₄₄H₃₂N₈Cu元素分析值(计算值)/%:C 71.72(71.77), H 4.36(4.38), N 15.27(15.22); UV-Vis(CH₂Cl₂), λ _max/nm(lg ε ):424(5.47), 543.5(4.27), 584.5(3.94)。

1.2.4 取代席夫碱铜金属卟啉的合成方法一:将0.74 g(1 mmol)四(对氨基苯基)铜金属卟啉溶于15 mL DMF中, 加入4 mmol取代苯甲醛, 微波反应。冷却至室温, 加入大量水, 二氯甲烷萃取3次, 有机相干燥后硅胶柱层析, 流动相为二氯甲烷, 收集紫红色带旋干得紫红色晶体。

方法二:将0.74 g(1 mmol)四(对氨基苯基)铜金属卟啉溶于15 mL DMF中, 加入4 mmol取代苯甲醛, 加热回流反应, 后处理方法一。实验结果如表1所示。

1.2.5 水杨醛席夫碱铜金属卟啉催化剂的制备水杨醛席夫碱铜金属卟啉催化剂的制备类似文献[20]报道的方法。将0.57 g(0.5 mmol)水杨醛席夫碱铜金属卟啉(化合物5)溶于15 mL二氯甲烷中, 加入15 mL含0.08 g(2 mmol)NaOH的甲醇溶液, 加入2 mmol乙酸铜, 回流反应0.5 h, 冷却析出大量固体, 抽滤得紫色固体。

2 结果与讨论

2.1 取代席夫碱铜金属卟啉化合物的表征

实验所得产品通过质谱、元素分析与紫外可见光谱表征。表征数据如表1所示。

表1 取代席夫碱铜金属卟啉表征结果 Table 1 The characterization of Cu(Ⅱ )meso-tetra(Schiff-base substituted phenyl)porphyrins

2.2 取代基对席夫碱铜金属卟啉化合物合成产率的影响

从表1可以看出, 微波条件大大加快了缩合反应速率, 所得卟啉的产率相对提高。取代苯甲醛与四(对氨基苯基)铜金属卟啉的缩合反应速率和产率与芳香醛取代基的性质有关, 含吸电子基团的芳香醛大于含给电子基团的芳香醛, 且随吸电子性的增强而增加, 随给电子性的增强而减少。可能是吸电子基团增强了芳香醛中羰基的活性, 使得氨基更容易进攻羰基碳, 然后脱去一分子水形成席夫碱。

2.3 取代席夫碱铜金属卟啉化合物紫外-可见光吸收光谱

图2为中性条件下取代基对席夫碱铜金属卟啉化合物的紫外-可见光吸收光谱, 四(对氨基苯基)铜金属卟啉的Soret带及取代席夫碱-铜金属卟啉的Soret带出现在424 nm左右。然而, 水杨醛席夫碱-铜金属卟啉的Soret带出现在421 nm, 羟基处于对位或间位的席夫碱-铜金属卟啉并未引起Soret带的紫移, 可能是邻位羟基和键与铜离子产生了某种作用, 侧链与铜离子间微弱的配位作用使得大环共轭体系的电子云密度有所降低, π 电子被激发所需的能量增加, Soret带发生了紫移。

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	图2 取代席夫碱铜金属卟啉化合物紫外-可见光吸收光谱Fig.2 The UV-Vis absorption of Cu(Ⅱ )meso-tetra(Schiff-base substituted phenyl)porphyrins

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	图3 水杨醛席夫碱铜金属卟啉与铜离子形成金属卟啉-铜配合物动力学过程Fig.3 The formation kinetics of salicylaldehyde schiff base metalloporphyrin-Cu complex from salicylaldehyde Schiff base metalloporphyrin

2.4 水杨醛席夫碱铜金属卟啉-铜配合物的形成动力学

图3为水杨醛席夫碱铜金属卟啉与铜离子形成金属卟啉-铜配合物动力学过程。从图3可知, 水杨醛席夫碱铜金属卟啉在氢氧化钠的作用下, 与铜离子再次发生反应, 体系紫外可见光吸收再次发生变化, Soret带强度不断下降, 从0.75降至0.46, 并发生红移, 从421.5 nm红移至425 nm。两个Q带发生红移, 分别为541 nm红移至545 nm, 578 nm红移至588 nm。可能是在氢氧化钠的作用下邻位羟基变成了酚氧负离子, 增加了亲核活性, 更有利于侧链与铜离子配位, 分子间配位形成复杂的配合物^[20], 同时酚氧负离子的给电子效应使得卟啉环共轭体系的电子云密度增大, π 电子被激发需要的能量降低, 因而紫外-可见光吸收光谱整体发生了红移。从Soret带和Q带可以断定, 当加入碱后, 金属卟啉中心铜并没有脱落, 否则Q带将变为4个, 此时侧链席夫碱上的羟基和N与铜离子发生配合, 可能具备新的化学活性。席夫碱金属配体是一类良好的催化剂^{[12, 13, 20]}, 铜金属卟啉亦有催化活性, 卟啉环的共轭效应又增加了体系的稳定性, 水杨醛席夫碱铜金属卟啉-铜配合物可能具备良好的催化效果。

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	图4 水杨醛席夫碱铜金属卟啉-铜配合物催化氧化环己烷Fig.4 Cyclohexane oxidation catalyzed by salicylaldehyde schiff base metalloporphyrin-Cu complex

2.5 水杨醛席夫碱铜金属卟啉-铜配合物催化氧化环己烷

近年来, 环己烷的催化氧化研究得到广泛关注^[24]。根据不同的催化剂, 其转化率在0.6%17%之间, 且对于转化率较高的催化剂, 环己酮的选择性最高只能达到48%^[25], 席夫碱金属卟啉类催化剂催化氧化环己烷的转化率及其对环己酮的选择性较为理想^[20]。本文将150 mL环己烷加入到反应瓶中, 加入水杨醛席夫碱铜金属卟啉-铜配合物催化剂, 通入O₂气, 10 min后加热保持80 ℃恒温, 每隔1 h取样1次, 样品处理后采用气相色谱仪分析, 反应30 h, 实验结果如图4所示。催化活性大小为:水杨醛席夫碱铜金属卟啉-铜配合物> 水杨醛席夫碱铜金属卟啉> CuTAPP, 且催化氧化150 mL环己烷所使用的水杨醛席夫碱铜金属卟啉-铜配合物催化剂的量以15 mg为宜, 环己烷的转化率达到了7.68%。从图1可以看出, 铜配体中心具有较高的催化活性, 而铜卟啉环中心可能为反应过程中产生的自由基提供了稳定的载体, 增强了自由基的存在时间, 从而使得自由基能充分发生有效反应, 催化剂过量可能会引起副反应的增加。另外, 图4中1~20 h段产率增速较慢, 20~25 h过程的产率增速较快, 可能是前期自由基浓度较低, 环己烷的自由基氧化速率较慢, 随着反应的进行, 且卟啉环共轭效应又保证了这些自由基的稳定存在性, 自由基浓度不断增大, 环己烷转化率提升较快。

表2 各时段的转化率及选择性 Table 2 The conversion and selectivity in different time

表2为15 mg水杨醛席夫碱铜金属卟啉-铜配合物催化氧化环己烷各时段的转化率及选择性。随着反应时间的进行, 环己烷的转化率不断提高, 环己酮的选择性不断增加, 环己醇的选择性有所降低, 副产物含量不断增加, 可能是环己醇被进一步氧化所致。常压条件下, 环己烷的催化氧化时间在24 h为宜。

关于水杨醛席夫碱铜金属卟啉-铜配合物催化氧化环己烷可能的机理如图5所示。高温条件下, O₂气、环己烷与催化剂中心铜离子产生某种中间体, 接着O— O键裂解产生环己基氧自由基与羟基自由基, 前者与环己烷作用产生环己醇与环己基自由基, 后者与卟啉环中心铜离子配位产生更稳定的自由基, 然后再与环己烷作用产生环己基自由基, 释放一分子水后变回水杨醛席夫碱铜金属卟啉-铜配合物催化剂。体系产生的环己基自由基与环己基过氧化氢作用产生环己基过氧自由基并释放一分子环己烷, 环己基自由基还可与氧分子形成环己基过氧自由基, 两分子环己基过氧自由基相互作用产生环己酮与环己醇并释放一分子氧^[25]。

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	图5 水杨醛席夫碱铜金属卟啉-铜配合物催化氧化环己烷可能的机理Fig.5 The possible mechanism of cyclohexane oxidation catalyzed by salicylaldehyde Schiff base metalloporphyrin-Cu complex

3 结论

取代苯甲醛与四(对氨基苯基)铜金属卟啉的缩合反应速率和产率与芳香醛取代基的性质有关, 含吸电子基团的芳香醛大于含给电子基团的芳香醛, 且随吸电子性的增强而增加, 随给电子性的增强而减少。微波反应能大大加快席夫碱卟啉的形成, 且产率有所提高。水杨醛席夫碱铜金属卟啉侧链在碱性条件下可与铜离子形成铜配合物, 其催化氧化环己烷的转化率可达到7.68%, 环己酮的选择性可达到60.87%。

参考文献

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[1]	Hayashi H, Lightcap I V, Tsujimoto M, et al. Electron Transfer Cascade by Organic/Inorganic Ternary Composites of Porphyrin, Zinc Oxide Nanoparticles, and Reduced Graphene Oxide on a Tin Oxide Electrode that Exhibits Efficient Photocurrent Generation[J]. J Am Chem Soc, 2011, 133(20): 7684-7687. [本文引用:1] [JCR: 10.677]
[2]	Wang Y, Cohen B, Jicsinszky L, et al. Femtosecond to Second Studies of a Water-Soluble Porphyrin Derivative in Chemical and Biological Nanocavities[J]. Langmuir, 2012, 28(9): 4363-4372. [本文引用:1] [JCR: 4.187]
[3]	Bonomo L, Lehaire M L, Solari E, et al. The First Crystalline Calcium Porphyrin and Tetrakis(tert-butylphenyl)porphyrinato Calcium(Ⅱ): Its Synthesis, Structure, and Binding Properties Towards Alkali and Alkaline Earth Metal Salts[J]. Angew Chem, 2001, 113(4): 793-796. [本文引用:1]
[4]	WANG Rongmin, PEI Fei, HE Yufeng, et al. Preparation and Biological Activitiy of Chitooligosaccharide Supported Porphyrins Metallic Complexes[J]. Chem Res Appl, 2012, 2: 278-281(in Chinese). 王荣民, 裴菲, 何玉凤, 等. 低聚壳聚糖负载金属卟啉配合物的制备及生物活性研究[J]. 化学研究与应用, 2012, 2: 278-281. [本文引用:1] [CJCR: 0.515]
[5]	YU Kegui, ZHOU Chenghe, LI Donghong. Recent Progress of the Porphyrin-based Anticancer Drugs[J]. Chem Res Appl, 2007, 12: 1296-1303(in Chinese). 于克贵, 周成合, 李东红. 卟啉类抗癌药物研究新进展[J]. 化学研究与应用, 2007, 12: 1296-1303. [本文引用:1] [CJCR: 0.515]
[6]	Zhou C Y, Chan P W, Che C M. Gold(Ⅲ) Porphyrin-Catalyzed Cycloisomerization of Allenones[J]. Org Lett, 2006, 8(2): 325-328. [本文引用:1] [JCR: 6.142]
[7]	Hasobe T, Fukuzumi S, Kamat P V. Organized Assemblies of Single Wall Carbon Nanotubes and Porphyrin for Photochemical Solar Cells: Charge Injection from Excited Porphyrin into Single-Walled Carbon Nanotubes[J]. J Phys Chem B, 2006, 110: 25477-25484. [本文引用:1] [JCR: 3.607]
[8]	McCratea A, Carloneb M, Nielsena M, et al. Anaerobic Photocleavage of Supercoiled DNA by a Ruthenium(Ⅱ) Substituted Fluorinated Porphyrin[J]. Inorg Chem Commun, 2010, 13(4): 537-539. [本文引用:1] [JCR: 2.016]
[9]	Yella Aswani, Lee Hsuan-Wei, Tsao Hoi Nok, et al. Porphyrin-Sensitized Solar Cells with Cobalt(Ⅱ/Ⅲ) Based Redox Electrolyte Exceed 12 Percent Efficiency[J]. Science, 2011, 334: 629-634. [本文引用:1]
[10]	Roy S, George C B, Ratner M A. Catalysis by a Zinc-Porphyrin-Based Metal-Organic Framework: From Theory to Computational Design[J]. J Phys Chem C, 2012, 116(44): 23494-23502. [本文引用:1] [JCR: 4.814]
[11]	Wu A S, Kiaei M Aguirre N, et al. Iron Porphyrin Treatment Extends Survival in a Transgenic Animal Model of Amyotrophic Lateral Sclerosis[J]. J Neurochem, 2003, 85: 142-150. [本文引用:1] [JCR: 3.973]
[12]	McGarrigle E M, Gilheany D G. Chromium and Manganese-salen Promoted Epoxidation of Alkenes[J]. Chem Rev, 2005, 105(5): 1563-1602. [本文引用:2] [JCR: 41.298]
[13]	FENG Huixia, GAO Xiaohong, CHEN Nali, et al. Catalytic Performance of Cobalt-Schiff Base-Chitosan/attapulgite for Epoxidation of Styrene[J]. Chinese J Appl Chem, 2014, 31(2): 159-164(in Chinese). 冯辉霞, 高晓红, 陈娜丽, 等. 钴-席夫碱-壳聚糖/凹凸棒土对苯乙烯环氧化的催化性能[J]. 应用化学, 2014, 31(2): 159-164. [本文引用:2] [CJCR: 0.741]
[14]	Kumar S, Dhar D N, Saxena P N, Kanpur I I T. Applications of Metal Complexes of Schiff Bases-A Review[J]. J Sci Ind Res, 2009, 68: 181-187. [本文引用:1] [JCR: 0.505]
[15]	Prakash A, Adhikari D. Application of Schiff Bases and Their Metal Complexes-A Review[J]. Int J Chem Tech Res, 2011, 3: 1891-1896. [本文引用:1]
[16]	XIE Fuxin, LIU Yuanfang, DONG Huaze, et al. Synthesis, Crystal Structure and Activity of Inhibiting Bacterium of a New Schiff Base[J]. Chinese J Med Chem, 2002, 12(5): 279-280(in Chinese). 谢复新, 刘远芳, 董华泽, 等. 一个新希夫碱的合成、晶体结构及抑菌活性[J]. 中国药物化学杂志, 2002, 12(5): 279-280. [本文引用:1] [CJCR: 0.471]
[17]	Callaway W B, Veauthier J M, Sessler J L. Schiff-base Porphyrin and Expand ed Porphyrin Analogs[J]. J Porphyr Phthalocya, 2004, 8: 1-25. [本文引用:1] [JCR: 1.433]
[18]	Wu Yahong, Chen Lin, Yu Jian, et al. Synthesis and Spectroscopic Characterization of meso-Tetra(Schiff-base substituted phenyl) porphyrins and Their Zinc Complexes[J]. Dyes Pigm, 2013, 97: 423-428. [本文引用:1]
[19]	CHEN Lin, TONG Shanling, WU Yahong, et al. Synthesis and Spectral Characters of meso-Tetra[4-(Benzylideneamino)phenyl] Porphyrin[J]. Chinese J Appl Chem, 2013, 30(3): 290-294(in Chinese). 陈林, 佟珊玲, 吴雅红, 等. Meso-四[(4-苯乙烯氨基)苯基]卟啉合成及其波谱特点[J]. 应用化学, 2013, 30(3): 290-294. [本文引用:1] [CJCR: 0.741]
[20]	SU Jianling, ZHAO Wenjun, ZHANG Fuchang, et al. Study of Complexes of Salen·porphyrin[J]. Appl Chem Ind, 2007, 36(4): 390-393(in Chinese). 苏建玲, 赵文军, 张富昌, 等. 新型Salen-卟啉金属配合物催化剂的研究[J]. 应用化工, 2007, 36(4): 390-393. [本文引用:4] [CJCR: 0.4349]
[21]	LUO Guotian, ZHENG Shengwei, XU Qingbing. Synthesis, Optical and Thermal Properties of Novel Schiff Base Complexes Containing Porphyin Copper(Ⅱ) and Zinc(Ⅱ)[J]. Chem J Chinese Univ, 2008, 29(7): 1307-1311(in Chinese). 罗国添, 郑生伟, 徐庆兵. 新型卟啉-席夫碱铜(Ⅱ)/锌(Ⅱ)配合物的合成与光热性能[J]. 高等学校化学学报, 2008, 29(7): 1307-1311. [本文引用:1] [JCR: 0.856] [CJCR: 0.949]
[22]	Imaoka T, Horiguchi H, Yamamoto K. Metal Assembly in Novel Dendrimers with Porphyrin Cores[J]. J Am Chem Soc, 2003, 125: 340-341. [本文引用:1] [JCR: 10.677]
[23]	Imaoka T, Tanaka R, Arimoto S, et al. Probing Stepwise Complexation in Phenylazomethine Dendrimers by a Metallo-Porphyrin Core[J]. J Am Chem Soc, 2005, 127: 13896-13905. [本文引用:1] [JCR: 10.677]
[24]	JING Shubo, WANG Guojia. Advances in Studies on Catalyst Research for Oxidation of Cyclohexane[J]. Spec Petrochem, 2004, 2: 52-57(in Chinese). 井淑波, 王国甲. 环己烷催化氧化进展[J]. 精细石油化工, 2004, 2: 52-57. [本文引用:1]
[25]	ZHANG Yicheng, DAI Weili, WU Guangjun, et al. Cyclohexane Oxidation: Small Organic Molecules as Catalysts[J]. Chinese J Catal, 2014, 35: 279-285(in Chinese). 张义成, 戴卫理, 武光军, 等. 环己烷氧化反应: 有机小分子的催化作用[J]. 催化学报, 2014, 35: 279-285. [本文引用:2] [JCR: 1.304] [CJCR: 1.178]

2011

10.677

0.0

Hayashi

, Lightcap I

, Tsujimoto

, et al. Electron Transfer Cascade by Organic/Inorganic Ternary Composites of Porphyrin, Zinc Oxide Nanoparticles, and Reduced Graphene Oxide on a Tin Oxide Electrode that Exhibits Efficient Photocurrent Generation[J]. J Am Chem Soc, 2011, 133(20): 7684-7687.

† Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan ‡ Radiation Laboratory, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States § Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan pkamat@nd.edu ; imahori@scl.kyoto-u.ac.jp

A bottom-up strategy has been developed to construct a multiple electron transfer system composed of organic/inorganic ternary composites (porphyrin, zinc oxide nanoparticles, reduced graphene oxide) on a semiconducting electrode without impairing the respective donor–acceptor components. The hierarchical electron transfer cascade system exhibited remarkably high photocurrent generation with an incident-photon-to-current efficiency of up to ca. 70%.

... 具备优异光电效应^[1]、特定生物功能^[2]、良好理化性能^[3]的有机大分子卟啉类化合物被广泛应用于生物科学、医药科学、材料科学、催化科学等领域^[4,5,6,7] ...

2012

4.187

0.0

Wang

, Cohen

, Jicsinszky

, et al. Femtosecond to Second Studies of a Water-Soluble Porphyrin Derivative in Chemical and Biological Nanocavities[J]. Langmuir, 2012, 28(9): 4363-4372.

† Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica, and INAMOL, Universidad de Castilla-La Mancha , Avenida Carlos III, S/N, 45071 Toledo, Spain ‡ Department of Synthesis, CYCLOLAB R&D Lab. Ltd. , IX. Illatos ut 7, H-1097 Budapest, Hungary *E-mail: Abderrazzak.Douhal@uclm.es . Fax: +34-925-268840 . Phone: +34-925-265717 .

The interactions of 5,10,15,20-tetrakis(4-sulfonatophenyl)-porphyrin (TSPP) with a quaternary ammonium modified β-cyclodextrin (QA-β-CD) and human serum albumin (HSA) protein in aqueous solutions at pH 7 were studied using steady-state, stopped-flow, and femtosecond to millisecond spectroscopy. TSPP forms 1:1 and 1:2 complexes with QA-β-CD ( K 1 = 1.9 × 10 5 M –1 and K 2 = 7 × 10 3 M –1 ) at 293 K, whereas with the HSA protein only 1:1 complex ( K 1 = 1.7 × 10 6 M –1 ) has been found. The chemical and biological nanocavities have notable effects on the fluorescence lifetimes of the Q x state (from 9.3 to 11.1 ns in QA-β-CD and 11.6 ns in HSA). Furthermore, the rotational times (400 ps for the free TSPP, 1.6 and 19 ns for QA-β-CD and HSA protein complexes, respectively) clearly indicate the robustness of the formed entities. The confined environment does not affect much the fs dynamics (0.1–0.2 ps) of the encapsulated molecule. However, it clearly affect the ps one (1–2 ps (H 2 O) and 5–10 ps (QA-β-CD and HSA)). The effect of O 2 on the relaxation of the triplet state of the free and encapsulated TSPP is also studied and the obtained results are discussed in light of the shielding effect provided by the chemical and biological cavities. The observed difference, longer triplet lifetime upon encapsulation, might be relevant to the efficiency of this porphyrin in photodynamic therapy. The presteady-state kinetics of the TSPP:HSA has been studied by the stopped-flow spectrometer, and a two-step model was proposed for the complexation processes. The results show the importance of the initial association step for the overall ligand recognition process. This first step occurs with rate constant of ∼4 × 10 5 M –1 s –1 , which is about 5 orders of magnitude larger than the rate constant of the consecutive relaxation processes. We believe that our observations of molecular interaction between TSPP, QA-β-CD, and HSA protein from femtosecond to second at both ground and electronically first excited state give detailed information to improve our understanding of this kind of system and thus for a better design of drug delivery nanocarriers.

2001

0.0

Bonomo

, Lehaire M

, Solari

, et al. The First Crystalline Calcium Porphyrin and Tetrakis(tert-butylphenyl)porphyrinato Calcium(Ⅱ): Its Synthesis, Structure, and Binding Properties Towards Alkali and Alkaline Earth Metal Salts[J]. Angew Chem, 2001, 113(4): 793-796.

Institut de Chimie Minérale et Analytique Université de Lausanne BCH, 1015 Lausanne (Switzerland) Fax: (+41) 21-6923905

2012

0.0

0.515

2007

0.0

0.515

Kegui

, ZHOU

Chenghe

, LI

Donghong.

Recent Progress of the Porphyrin-based Anticancer Drugs[J]. Chem Res Appl, 2007, 12: 1296-1303(in Chinese).

于克贵, 周成合, 李东红. 卟啉类抗癌药物研究新进展[J]. 化学研究与应用, 2007, 12: 1296-1303.

本文对目前以卟啉为基础的抗癌药物进行了综述,主要阐述了临床上或临床前试验中卟啉类抗癌药物新进展与构效关系.

2006

6.142

0.0

Zhou C

, Chan P

, Che C

Gold(Ⅲ) Porphyrin-Catalyzed Cycloisomerization of Allenones[J]. Org Lett, 2006, 8(2): 325-328.

Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong

Gold(III) porphyrin-catalyzed cycloisomerization of allenones gave the corresponding furans in good to excellent yields (up to 98%) and with quantitative substrate conversions. By recovering the Au(III) catalyst, a recyclable catalytic system is developed with over 8300 product turnovers attained for the cycloisomerization of 1-phenyl-buta-2,3-dien-1-one. The versatility of the gold(III) porphyrin catalyst was exemplified by its application to the hydroamination and hydration of phenylacetylene in 73% and 87% yield, respectively.

2006

3.607

0.0

Hasobe

, Fukuzumi

, Kamat P

Organized Assemblies of Single Wall Carbon Nanotubes and Porphyrin for Photochemical Solar Cells: Charge Injection from Excited Porphyrin into Single-Walled Carbon Nanotubes[J]. J Phys Chem B, 2006, 110: 25477-25484.

Radiation Laboratory and Departments of Chemistry & Biochemistry and Chemical & Biomolecular Engineering, University of Notre Dame, Notre Dame, Indiana 46556, and Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, SORST, Japan Science and Technology Agency, Suita, Osaka 565-0871, Japan

Photochemical solar cells have been constructed from organized assemblies of single-walled carbon nanotubes (SWCNT) and protonated porphyrin on nanostructured SnO 2 electrodes. The protonated form of porphyrin (H 4 P 2+ ) and SWCNT composites form 0.5−3.0 μm-sized rodlike structures and they can be assembled onto nanostructured SnO 2 films [optically transparent electrode OTE/SnO 2 ] by an electrophoretic deposition method. These organized assemblies are photoactive and absorb strongly in the entire visible region. The incident photon to photocurrent efficiency (IPCE) of OTE/SnO 2 /SWCNT-H 4 P 2+ is ∼13% at an applied potential of 0.2 V versus saturated calomel electrode. Femtosecond pump−probe spectroscopy experiments confirm the decay of the excited porphyrin in the SWCNT−H 4 P 2+ assembly as it injects electrons into SWCNT. The dual role of SWCNT in promoting photoinduced charge separation and facilitating charge transport is presented.

2010

2.016

0.0

McCratea

, Carloneb

, Nielsena

, et al. Anaerobic Photocleavage of Supercoiled DNA by a Ruthenium(Ⅱ) Substituted Fluorinated Porphyrin[J]. Inorg Chem Commun, 2010, 13(4): 537-539.

... 人们不断研究新型功能型卟啉并将其应用于切割DNA、太阳能电池、工业催化剂甚至动物饲料上^[8,9,10,11] ...

2011

0.0

Yella

Aswani

, Lee

Hsuan-Wei

, Tsao Hoi

Nok

, et al. Porphyrin-Sensitized Solar Cells with Cobalt(Ⅱ/Ⅲ) Based Redox Electrolyte Exceed 12 Percent Efficiency[J]. Science, 2011, 334: 629-634.

1 Laboratory for Photonics and Interfaces, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne,Lausanne-1015, Switzerland. 2 Department of Chemistry and Center of Nanoscience and Nanotechnology, National Chung Hsing University, Taichung, Taiwan 402,ROC. 3 Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu, Taiwan 300, ROC. ↵ *To whom correspondence should be addressed. E-mail: michael.graetzel@epfl.ch (M.G.); shaik.zakeer@epfl.ch (S.M.Z.); diau@mail.nctu.edu.tw (E.W.-G.D); cyyeh@dragon.nchu.edu.tw (C.-Y.Y.)

... 人们不断研究新型功能型卟啉并将其应用于切割DNA、太阳能电池、工业催化剂甚至动物饲料上^[8,9,10,11] ...

2012

4.814

0.0

Roy

, George C

, Ratner M

Catalysis by a Zinc-Porphyrin-Based Metal-Organic Framework: From Theory to Computational Design[J]. J Phys Chem C, 2012, 116(44): 23494-23502.

Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States *E-mail: sharani-roy@northwestern.edu .

Catalytic metal–organic frameworks (MOFs) have captured widespread attention for displaying shape, size, chemical, and enantiomeric selectivity characteristic of biological enzymes. Nguyen and co-workers [ J. Am. Chem. Soc. 2009 , 131 , 4204–4205] synthesized a stable, crystalline, microporous, zinc-porphyrin-based metal–organic framework (ZnPO-MOF) that incorporates the catalytic activity of metalloporphyrins. They observed a 236-fold initial acceleration of an acyl-transfer reaction between 3-pyridylcarbinol and N -acetylimidazole by ZnPO-MOF, and attributed this catalysis primarily to a high local concentration or “preconcentration” of reactants at the porphyrin-Zn active sites of the framework. We report a detailed theoretical investigation of the framework-promoted reaction using the full atomic structure of the MOF. The three-step first-principles-based method developed for this purpose can be applied to study other catalytically active MOFs, and can help in the computational design of frameworks with optimum preconcentration and chemical sensing properties. Calculations show that reactants bind to the closely packed porphyrin-Zn sites of ZnPO-MOF, resulting in a high local concentration of catalyst-bound reactant. Our model predicts that reactant preconcentration in ZnPO-MOF can increase the initial rate of the acyl-transfer reaction by about 2 orders of magnitude relative to the uncatalyzed reaction, and can be the dominant catalytic mechanism in this system.

... 人们不断研究新型功能型卟啉并将其应用于切割DNA、太阳能电池、工业催化剂甚至动物饲料上^[8,9,10,11] ...

2003

3.973

0.0

Wu A

, Kiaei M Aguirre N, et al. Iron Porphyrin Treatment Extends Survival in a Transgenic Animal Model of Amyotrophic Lateral Sclerosis[J]. J Neurochem, 2003, 85: 142-150.

1 Department of Neurology and Neuroscience, Weill Medical College of Cornell University, New York, USA 2 Departments of Anesthesiology, Pharmacology/Toxicology, and Biochemistry and Molecular Genetics, University of Alabama at Birmingham, Birmingham, Alabama, USA * Address correspondence and reprint requests to M. Flint Beal, Department of Neurology and Neuroscience, Weill Medical College of Cornell University, New York, NY 10021, USA. E-mail: fbeal@med.cornell.edu

> Oxidative damage, produced by mutant Cu/Zn superoxide dismutase (SOD1), may play a role in the pathogenesis of amyotrophic lateral sclerosis (ALS), a devastating motor neuron degenerative disease. A novel approach to antioxidant therapy is the use of metalloporphyrins that catalytically scavenge a wide range of reactive oxygen and reactive nitrogen species. In this study, we examined the therapeutic potential of iron porphyrin (FeTCPP) in the G93A mutant SOD1 transgenic mouse model of ALS. We found that intraperitoneal injection of FeTCPP significantly improved motor function and extended survival in G93A mice. Similar results were seen with a second group of mice wherein treatment with FeTCPP was initiated at the onset of hindlimb weakness—roughly equivalent to the time at which treatment would begin in human patients. FeTCPP-treated mice also showed a significant reduction in levels of malondialdehyde (a marker of lipid peroxidation), in total content of protein carbonyls (a marker of protein oxidation), and increased neuronal survival in the spinal cord. These results therefore provide further evidence of oxidative damage in a mouse model of ALS, and suggest that FeTCPP could be beneficial for the treatment of ALS patients.

... 人们不断研究新型功能型卟啉并将其应用于切割DNA、太阳能电池、工业催化剂甚至动物饲料上^[8,9,10,11] ...

2005

41.298

0.0

McGarrigle E

, Gilheany D

. Chromium and Manganese-salen Promoted Epoxidation of Alkenes[J]. Chem Rev, 2005, 105(5): 1563-1602.

Chemistry Department, Centre for Synthesis and Chemical Biology, Conway Institute of Biomolecular and Biomedical Sciences, University College Dublin, Belfield, Dublin 4, Ireland

... 席夫碱及其金属配合物被视为一种高效催化剂,大大提高了烯烃催化环氧化产率^[12,13],同时席夫碱还被视为一类高活性抑菌剂^[14,15,16] ...

... 席夫碱金属配体是一类良好的催化剂^[12,13,20],铜金属卟啉亦有催化活性,卟啉环的共轭效应又增加了体系的稳定性,水杨醛席夫碱铜金属卟啉-铜配合物可能具备良好的催化效果 ...

2014

0.0

0.741

FENG

Huixia

, GAO

Xiaohong

, CHEN

Nali

, et al. Catalytic Performance of Cobalt-Schiff Base-Chitosan/attapulgite for Epoxidation of Styrene[J]. Chinese J Appl Chem, 2014, 31(2): 159-164(in Chinese).

冯辉霞, 高晓红, 陈娜丽, 等. 钴-席夫碱-壳聚糖/凹凸棒土对苯乙烯环氧化的催化性能[J]. 应用化学, 2014, 31(2): 159-164.

With the Schiff base of L-aspartic acid and salicylaldehyde as the ligands, the composite resin of chitosan/attapulgite(CS/ATP) produced by NaOH curing method as the carrier, the Schiff base metal complexes and the load-type Schiff base metal complexes of Co, Mn, Cu, Fe, Ni were synthesized. Their structural characterizations were determined by FT-IR. The catalytic performance of each catalyst for epoxidation of styrene was studied. Experiments show that the catalytic performance of Co-Schiff base is better in small molecule ligand Schiff base metal complexes. Therefore, Co-Schiff base was loaded in CS/ATP composite resin and the effects of the amount of Co-Schiff base-CS/ATP catalyst, reaction temperature and reaction time on the catalytic epoxidation of styrene were investigated. Finally the results show that the best reaction conditions are as follows:the temperature is 80 ℃ and the reaction time is 8 h, which results in a conversion rate of 93.1% for epoxidation of styrene.

(College of Petrochemical Engineering，Lanzhou University of Technology，Lanzhou 730050,China)

以NaOH固化法制备的壳聚糖/凹凸棒土（CS/ATP）复合树脂为载体，以水杨醛和天冬氨酸合成的席夫碱为配体，分别合成Co、Mn、Cu、Fe和Ni的席夫碱金属配合物及其负载型席夫碱金属配合物，并通过FT-IR对其进行结构表征，且以苯乙烯为底物，分子氧为氧源，分别考察了各种催化剂对苯乙烯的环氧化性能。实验结果表明，在小分子席夫碱金属配体中，Co-Schiff碱催化性能较好。将Co-Schiff碱负载到CS/ATP复合树脂中，综合考察了Co-Schiff碱-CS/ATP的用量、温度、时间对苯乙烯催化环氧化性能的影响，结果表明，反应温度为80 ℃，反应时间为8 h，苯乙烯的转化率达93.1%。

... 席夫碱及其金属配合物被视为一种高效催化剂,大大提高了烯烃催化环氧化产率^[12,13],同时席夫碱还被视为一类高活性抑菌剂^[14,15,16] ...

2009

0.505

0.0

... 席夫碱及其金属配合物被视为一种高效催化剂,大大提高了烯烃催化环氧化产率^[12,13],同时席夫碱还被视为一类高活性抑菌剂^[14,15,16] ...

2011

0.0

... 席夫碱及其金属配合物被视为一种高效催化剂,大大提高了烯烃催化环氧化产率^[12,13],同时席夫碱还被视为一类高活性抑菌剂^[14,15,16] ...

2002

0.0

0.471

XIE

Fuxin

, LIU

Yuanfang

, DONG

Huaze

, et al. Synthesis, Crystal Structure and Activity of Inhibiting Bacterium of a New Schiff Base[J]. Chinese J Med Chem, 2002, 12(5): 279-280(in Chinese).

谢复新, 刘远芳, 董华泽, 等. 一个新希夫碱的合成、晶体结构及抑菌活性[J]. 中国药物化学杂志, 2002, 12(5): 279-280.

合成了一个新型希夫碱,测定了该化合物的晶体结构:单斜晶系,空间群P21/n,a=13.325 6 (A),b=6.977 5 (A),c=13.940 2 (A),α=90°,β=113.881°,γ=90°,V=1 185.18((A))3,Z=4,Dc=1.524 g/cm3,R=0.073.抑菌试验表明:该希夫碱对金黄色葡萄球菌有深度的抑制作用.

... 席夫碱及其金属配合物被视为一种高效催化剂,大大提高了烯烃催化环氧化产率^[12,13],同时席夫碱还被视为一类高活性抑菌剂^[14,15,16] ...

2004

1.433

0.0

2013

0.0

Yahong

, Chen

Lin

, Yu

Jian

, et al. Synthesis and Spectroscopic Characterization of meso-Tetra(Schiff-base substituted phenyl) porphyrins and Their Zinc Complexes[J]. Dyes Pigm, 2013, 97: 423-428.

... 近年来,席夫碱卟啉类化合物得到了广泛关注^[18,19],在工业催化^[20]、分析科学^[21]以及功能大分子^[22,23]等领域应用广泛,研究席夫碱金属卟啉的合成与性质意义重大 ...

2013

0.0

0.741

CHEN

Lin

, TONG

Shanling

, WU

Yahong

, et al. Synthesis and Spectral Characters of meso-Tetra[4-(Benzylideneamino)phenyl] Porphyrin[J]. Chinese J Appl Chem, 2013, 30(3): 290-294(in Chinese).

陈林, 佟珊玲, 吴雅红, 等. Meso-四[(4-苯乙烯氨基)苯基]卟啉合成及其波谱特点[J]. 应用化学, 2013, 30(3): 290-294.

Using pyrrole and p-nitrobenzaldehyde as the starting materials, a novel conjugated product of meso-tetra[4-(benzylideneamino)phenyl] porphyrin(TBAPP) was designed and synthesized after cyclization, reduction and condensation reactions. The product was characterized by UV-Vis, FT-IR, 1H NMR determinations and elemental analysis. In addition, this porphyrin product was also investigated by fluorescence(FL) and electron paramagnetic resonance(EPR) methods. EPR measurement indicated that the prepared porphyrin molecule exhibited radical characteristics. The radicals were produced by the peripheral groups, which could be stabilized by the conjugated π-electrons of porphyrin molecule and detected under normal conditions. Meanwhile the substituent groups around the porphyrin ring contributed different influences on the spectral characters of UV-visible, fluorescence and electron paramagnetic resonance. Compare with its precursor of tetra-aminophenyl porpyrin(TAPP) and its parent compound of tetra-nitrophenyl porpyrin(TNPP), Q bands of the Schiff base phenyl porphyrin TBAPP shifted towards red direction, while its Soret band kept changeless; meanwhile, under excitation at λEx=440 nm, its emission peak appeared at λEm=658 nm, with 5 nm and 9 nm blue shift than those of TAPP and TNPP; furthermore its EPR fine structure was weaker than TAPP and stronger than TNPP.

(Faculty of Light Industry and Chemical Engineering,Guangdong University of Technology,Guangzhou 510006,China)

以吡咯和对硝基苯甲醛为原料,经过环化、还原和缩合,合成了meso-四[(4-苯乙烯氨基)苯基]卟啉(TBAPP),通过UV-Vis、FT-IR、1H NMR及元素分析等对产物进行了表征,并对其荧光和电子顺磁共振特性进行了研究。卟啉产物的EPR测定显示出游离基特征,表明卟啉分子的大π共轭结构对周边基团产生的自由基有稳定作用。取代基对卟啉的紫外可见吸收、光致发光及电子顺磁共振特性均有影响。四席夫碱苯基卟啉TBAPP的Q带比前体四氨基卟啉（TAPP）和母体四硝苯基卟啉（TNPP）红移，而Soret谱带变化较小；TBAPP的440 nm光激发的最大荧光峰658 nm分别比TAPP蓝移5 nm和比TNPP红移9 nm;TBAPP的EPR精细结构比TAPP弱，而比TNPP强。

2007

0.0

0.4349

... 可能是在氢氧化钠的作用下邻位羟基变成了酚氧负离子,增加了亲核活性,更有利于侧链与铜离子配位,分子间配位形成复杂的配合物^[20],同时酚氧负离子的给电子效应使得卟啉环共轭体系的电子云密度增大,π ...

... 6%17%之间,且对于转化率较高的催化剂,环己酮的选择性最高只能达到48%^[25],席夫碱金属卟啉类催化剂催化氧化环己烷的转化率及其对环己酮的选择性较为理想^[20] ...

2008

0.856

0.949

LUO

Guotian

, ZHENG

Shengwei

, XU

Qingbing.

Synthesis, Optical and Thermal Properties of Novel Schiff Base Complexes Containing Porphyin Copper(Ⅱ) and Zinc(Ⅱ)[J]. Chem J Chinese Univ, 2008, 29(7): 1307-1311(in Chinese).

罗国添, 郑生伟, 徐庆兵. 新型卟啉-席夫碱铜(Ⅱ)/锌(Ⅱ)配合物的合成与光热性能[J]. 高等学校化学学报, 2008, 29(7): 1307-1311.

5-( p -Benzylideneamino)phenyl-10, 15, 20-triphenylporphyrin copper(Ⅱ), zinc(Ⅱ) complexes and 5-[ p -(4-nitrobenzylideneamino)]phenyl-10, 15, 20-triphenylporphyrin copper(Ⅱ), zinc(Ⅱ) complexes were designed and synthesized by the reaction of pyrrole and benzaldehyde et al .. The intermediates and target compounds were characterized by FTIR, FAB-MS, UV-Vis spectra and 1 H NMR. Furthermore, one of the target compounds was confirmed by single crystal X-ray diffraction.In addition, we also studied the thermostability and luminescent effect of the target compounds.The experiment results show that the strongest luminescent wavelength is 600 nm, which locates in the visible light area. The compounds decompose at 70 ℃ in the air.

College of Chemistry and Life Science, Gannan Normal University, Ganzhou 341000, China

以吡咯、取代苯甲醛等为原料合成了5-(对-亚苄基亚氨基)苯基-10,15,20-三苯基卟啉的铜(Ⅱ)/锌(Ⅱ)配合物和5-[对-(4-硝基亚苄基亚氨基)]苯基-10,15,20-三苯基卟啉的铜(Ⅱ)/锌(Ⅱ)配合物. 通过FTIR, UV-Vis, 1 H NMR, FAB-MS及X射线单晶衍射等手段对产物进行了表征, 并研究了其发光性能及热稳定性. 实验结果表明, 合成配合物的最大发光波长为600 nm, 位于可见光中的红光区; 化合物在空气中的初始分解温度为70 ℃.

2003

10.677

0.0

Imaoka

, Horiguchi

, Yamamoto

Metal Assembly in Novel Dendrimers with Porphyrin Cores[J]. J Am Chem Soc, 2003, 125: 340-341.

Kanagawa Academy of Science & Technology (KAST), Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama 223-8522, Japan

A series of phenylazozmethine (DPA) dendrimers with a porphyrin core (P n H 2 ) were synthesized by dehydration using TiCl 4 from meso -tetrakis(4-aminophenyl)porphyrin and the DPA dendrons. The addition of SnCl 2 to a dichloromethane/acetonitrile solution of dendritic cobalt porphyrin resulted in a stepwise spectral change. By using UV−vis spectroscopy to monitor the complexation of the P 4 Co III Cl until an equimolar amount of SnCl 2 has been added, four changes in the position of the isosbestic point were observed during the addition of SnCl 2 . Titration results suggest that four different complexes are successively formed upon the SnCl 2 addition and that the complexation proceeds in, not a random, but a stepwise fashion from the core imines to the terminal imines of P 4 Co III Cl. The electrochemical study reveals that their dendrimers with Tb ion act as a multielectron mediator in CO 2 reduction at high applied potential on the electrode.

2005

10.677

0.0

Imaoka

, Tanaka

, Arimoto

, et al. Probing Stepwise Complexation in Phenylazomethine Dendrimers by a Metallo-Porphyrin Core[J]. J Am Chem Soc, 2005, 127: 13896-13905.

Contribution from the Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama 223-8522, Japan, and Chemical Resources Laboratory, Tokyo Institute of Technology, Yokohama 226-8503, Japan

A series of dendritic phenylazomethines (DPA), which have a meso -substituted zinc porphyrin core ( DPAGX-ZnP , X = 1−4), were synthesized. Structural studies of these dendrimers were carried out using Tri-SEC (triple detection after size exclusion chromatography), intrinsic viscosity analysis, TEM (tunneling electron microscopy), and molecular modeling calculations by AM1. As a result, a sphere-like structure within a single-nanometer scale ( R h = 22 Å for DPAG4-ZnP ) was observed. In addition, encapsulating effects by the DPA shell in the larger dendrimers were confirmed as fundamental properties, based on the UV−vis abosorption spectra, cyclic voltammograms, and 1 H NMR spin−lattice relaxation times ( T 1 ). The DPAGX-ZnP acts as a multi-metal ion reservoir for SnCl 2 and FeCl 3 . The generation-4 dendrimer ( DPAG4-ZnP ) can take up to 60 molar amounts of metal complexes around the porphyrin core. A quantitative study of the metal assembling reaction by UV−vis titration revealed stepwise layer-by-layer complexations from the inner imines nearest to the core to the surface. The redox behavior and fluorescence of the zinc porphyrin in these metal-assembled dendrimers also support the stepwise complexation of the metal ion. These analyses suggest that the finely assembled metal complexes in a dendrimer architecture strongly affect the electronic status of the porphyrin core. Results from transient absorption measurements strongly indicate a very fast electron transfer on a subpicosecond time scale between the core and assembled metal complexes.

2004

0.0

JING

Shubo

, WANG

Guojia.

Advances in Studies on Catalyst Research for Oxidation of Cyclohexane[J]. Spec Petrochem, 2004, 2: 52-57(in Chinese).

井淑波, 王国甲. 环己烷催化氧化进展[J]. 精细石油化工, 2004, 2: 52-57.

综述了环己烷催化氧化反应的研究进展,分别介绍了Gif体系、卟啉及其他配合物体系、酞菁体系、金属取代的杂多化合物体系、分子筛体系、N-邻苯二甲酸酰氨/过渡金属配合物体系及纳米金属氧化物体系催化剂在该反应中的应用.

... 5 水杨醛席夫碱铜金属卟啉-铜配合物催化氧化环己烷近年来,环己烷的催化氧化研究得到广泛关注^[24] ...

2014

1.304

1.178

ZHANG

Yicheng

, DAI

Weili

, WU

Guangjun

, et al. Cyclohexane Oxidation: Small Organic Molecules as Catalysts[J]. Chinese J Catal, 2014, 35: 279-285(in Chinese).

张义成, 戴卫理, 武光军, 等. 环己烷氧化反应: 有机小分子的催化作用[J]. 催化学报, 2014, 35: 279-285.

The catalytic activity of several small organic molecules including ketones, aldehydes, esters, alcohols and amines toward cyclohexane oxidation was investigated. The catalytic activity was found to be closely related to polarity, α-H activity, the strength of hydrogen bond formed with cyclohexane and the radical scavenging capability of these molecules. Based on the obtained results, the catalytic role of the organic solvent must be considered for cyclohexane oxidation. Tripropylamine has very high activity in cyclohexane oxidation and it might be further developed as a promising small-molecule organocatalyst for future application.

Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China

考察了酮、醛、酯、醇与胺等几类有机小分子在环己烷氧化反应中的催化作用. 结果表明，有机小分子催化剂的活性与其极性的强弱、与环己烷形成氢键的强弱、α氢的活性及清除自由基的能力有关. 因此，对于环己烷氧化反应，溶剂很可能存在催化作用. 三丙胺在环己烷氧化反应中表现出较高的催化活性，具有进一步开发应用的前景.

... 体系产生的环己基自由基与环己基过氧化氢作用产生环己基过氧自由基并释放一分子环己烷,环己基自由基还可与氧分子形成环己基过氧自由基,两分子环己基过氧自由基相互作用产生环己酮与环己醇并释放一分子氧^[25] ...