两种A2B型咔咯化合物的合成及表征

以5-(3-硝基苯基)二吡咯甲烷与2,4-二氯基苯甲醛或2,4-二甲氧基苯甲醛为原料,在水和甲醇溶剂中采用改进的Lindsey法合成了标题化合物,测定了化合物的紫外-可见及荧光光谱,用红外、核磁共振、质谱等技术对化合物的结构进行了表征,结果表明所得产物即为目标配合物。     

咔咯化学研究的新进展

简要介绍了咔咯化学的产生、发展、结构特征及应用。重点介绍了:(1)新型咔咯配合物的合成及在催化科学中的应用;(2)新型咔咯配合物的合成及在医学中的应用;(3)新型金属咔咯配合物的合成及在材料科学和光化学方面的应用。并对咔咯化学的发展进行了展望。     

金属-卟啉框架材料在光催化领域的应用

金属-有机框架(metal-organic frameworks,MOFs)是一种由金属离子或金属簇与多齿有机配体通过配位键连接而形成的有机无机杂化多孔晶态材料,具有较大的比表面积和孔道,同时结构也易于实现剪裁。近十几年MOFs在催化、气体吸附等领域得到了较大发展。卟啉等四吡咯大环结构有很好的光吸收特性,作为连接体应用于MOFs中可有效拓宽其吸收光谱,因此,基于卟啉配体的MOFs被广泛应用于光催化领域。本文综述了近十年来金属-卟啉框架材料在光催化选择性有机合成、析氢、析氧、还原CO₂、降解有机污染物方面的应用,同时对金属-卟啉框架材料未来在光催化领域的发展进行了展望。     

Pyrolyzed Cobalt Corrole as a Potential Non‐Precious Catalyst for Fuel Cells

Non‐precious metal catalysts of the oxygen reduction reaction are highly favored for use in polymer electrolyte fuel cells (PEFC) because of their relatively low cost. Here, a new carbon‐black‐supported pyrolyzed Co‐corrole (py‐Co‐corrole/C) catalyst of the oxygen reduction reaction (ORR) in a PEFC cathode is demonstrated to have high catalytic performance. The py‐Co‐corrole/C at 700 °C exhibits optimized ORR activity and participates in a direct four‐electron reduction pathway for the reduction of O₂ to H₂O. The H₂‐O₂ PEFC test of py‐Co‐corrole/C in the cathode reveals a maximum power density of 275 mW cm^?2, which yields a higher performance and a lower Co loading than previous studies of Co‐based catalysts for PEFCs. The enhancement of the ORR activity of py‐Co‐corrole/C is attributable to the four‐coordinated Co‐corrole structure and the oxidation state of the central cobalt.     

Paul Rothemund and S. Ferguson MacDonald,and their Namesake Reactions – The Influence of the Fischer School on my Life in Porphyrin Chemistry

The Rothemund reaction and the MacDonald 2+2 condensation are two named reactions widely recognized in porphyrin syntheses. Yet not much has been written about the persons whose work paved the way to various porphyrins and porphyrinoids now realized. Paul Rothemund and S. Ferguson MacDonald both obtained their doctorate under Hans Fischer at Munich. Here I attempt to piece together the life stories of the two chemists, tracing back to the connections with the Fischer School, and giving the historical context to their namesake reactions. The pioneering discoveries of Fischer and his students, with later modifications, have become standard methods in the modern era for the synthesis of sizable quantities of porphyrins and porphyrinoids employed for enzyme models, catalysts, drugs, sensors, and building blocks of materials and biomedical research. This essay highlights the pioneers’ achievements, renders history relevant, and recounts the influence they had on my research.     

多功能咔咯配合物的合成与应用进展

咔咯(Corrole)是由4个吡咯共轭相连而形成的新型卟啉类大环配合物,它们能稳定结合具有较高氧化态的金属离子,所形成的金属配合物具有比较独特的光化学、电化学、光物理和光生物性质。研究表明,咔咯是一类非常重要的多功能配合物,它们在精细化学品领域具有广阔的应用前景。对咔咯配合物的主要合成方法、配合物用作精细化工催化剂、燃料电池电极催化材料、抗肿瘤光敏剂、电化学传感器和非线性光学材料等方面的研究和应用作了综述。     

Gold(III) Corroles for High Performance Organic Solar Cells

While the use of molecular materials having long‐lived triplet excited state(s) for harvesting solar energy could be an effective approach to boost up the power conversion efficiency (PCE) of organic solar cells (OSCs), the performances of this kind of OSCs as reported in the literature are low (< 2.9% PCE attained for the vacuum‐deposited OSCs). Herein is described the realization of high performance OSCs by using gold(III) 5,10,15‐triphenylcorrole ( Au‐C1 ), gold(III) 10‐(p‐trifluoromethylphenyl)‐5,15‐diphenylcorrole ( Au‐C2 ), and gold(III) 10‐(pentafluorophenyl)‐5,15‐diphenyl‐corrole ( Au‐C3 ), as electron‐donors. These gold(III) corroles display excited state lifetimes of ≥ 25 μs and low emission quantum yields of < 0.15%. With the complexes Au‐C1 , Au‐C2 , and Au‐C3 , vacuum‐deposited OSCs, which give PCEs of 2.7%, 3.0%, and 1.8%, respectively, are fabricated. The PCE can be further boosted up to 4.0% after thermal treatment of the OSC devices. Meanwhile, a solution‐processed OSC based on Au‐C2 with a high PCE of 6.0% is fabricated. These PCE values are among the best reported for both types of vacuum‐deposited and solution‐processed OSCs fabricated with metal‐organic complexes having long‐lived excited states as electron‐donor material. The underlying mechanism for the inferior performance of the reported OSCs is discussed.     

两种甲氧基苯基咔咯配合物的合成与表征

以吡咯和甲氧基苯甲醛为反应起始物,在水和甲醇溶剂中采用改进的Lindsey法合成了4-甲氧基苯基咔咯(a)和2,4-二甲氧基苯基咔咯(b)两种无金属甲氧基苯基咔咯配合物.测定了配合物在二氯甲烷溶剂中的紫外-可见及荧光光谱.发现配合物a和b的Soret分别位于418和420 nm,Q吸收峰则分别位于570、608、645...     

3，5-二乙基-2，4-二甲氧羰基吡咯的合成

在制备八乙基咔咯的过程中,得到了一种新的化合物3,5-二乙基-2,4-二甲氧羰基吡咯。它是以丙酰乙酸甲酯为原料,经过亚硝化、还原、与原料自身通过Knorr反应制得产物。研究了不同的反应条件对产率的影响,并提出了最佳反应条件。通过熔点测定、IR和^1HNMR光谱对产物进行了表征。     

咔咯锰、铁和钴配合物的合成与应用研究进展

金属咔咯是具有独特的光化学、光物理、光生物性质的多功能卟啉类配合物。特别是一些含有过渡金属如锰、铁、钴为中心离子的金属咔咯配合物,在新型催化剂、抗肿瘤药物、电化学传感器以及纳米材料等领域都具有较好的应用前景。对含有锰、铁、钴中心金属离子的单核和双核咔咯配合物的合成方法及在相关领域的应用进展进行了综述,为该类配合物的进一步研究和应用提供有益参考。