共查询到14条相似文献,搜索用时 93 毫秒
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以功能化氮配体为导向,以4,7-二苯基-1,10-菲咯啉为原料,经季铵化、氧化、卤化和醚化合成了一类新型的2,9-二烷氧基-4,7-二苯基-1,10-菲咯啉配体5a~5e。再以Xantphos为膦配体,通过原位配位方法合成一系列氮磷杂配铜光敏剂(CuPS A~H),在均相光解水制氢体系中研究其光敏活性。制氢结果表明,以2,9-二乙氧基为较佳取代基,CuPS D的催化产氢总转换数(TON)可达270。在光电物理性能分析中,发现这类杂配铜配合物都有一个相似的氧化还原电位(Eoxd=-0.8 V,Ered=-1.2 V)。具有乙氧取代基的铜配合物CuPS D相对于其他取代基的铜基配合物,荧光最弱,表明乙氧基有助于提高荧光淬灭效率,增强铜光敏剂的光化学转换能力。 相似文献
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以功能化氮配体为导向,以4,7-二苯基-1,10-菲咯啉为原料,经季铵化、氧化、卤化和醚化合成了一类新型的2,9-二烷氧基-4,7-二苯基-1,10-菲咯啉配体5a~5e。再以Xantphos为膦配体,通过原位配位方法合成一系列氮磷杂配铜光敏剂(Cu PS A~H),在均相光解水制氢体系中研究其光敏活性。制氢结果表明,以2,9-二乙氧基为较佳取代基,Cu PS D的催化产氢总转换数(TON)可达270。在光电物理性能分析中,发现这类杂配铜配合物都有一对相似的氧化还原电位(Eoxd=-0.8 V,Ered=-1.2 V)。具有乙氧取代基的铜配合物CuPSD相对于其他取代基的铜基配合物,荧光最弱,表明乙氧基有助于提高荧光淬灭效率,增强铜光敏剂的光化学转换能力。 相似文献
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设计、合成了一类4,7位为大环芳烃的菲咯啉二齿氮配体,可与铜.和Xantphos原位配位,获得一系列新型氮磷杂配铜光敏剂CuPS 1~CuPS 6,在均相光解水制氢体系中研究其光敏活性及构效关系。实验结果表明,在菲咯啉4,7位引入芳基有利于提高其光敏活性,1-萘基取代的CuPS 3有最好的制氢活性,光解水制氢转化数(TON)达957。通过理论计算对比分析,1-萘基取代基与菲咯啉母核具有较大的二面角,对铜配合物的激发态有较好的保护作用,因此CuPS 3表现出较高的荧光量子产率(0.036)和较长的激发态寿命(1.36μs)。 相似文献
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Crystal structure of the title compound, Cu(phen)(H2O)2·ClO4(phen=1,10-phenanthroline), was deter-mined by X-ray crystallography. It crystallizes in the monoclinic system, space group C2/c with lattice parameters a=1.49071(4)nm, b=1.38594(4)nm, c=0.70292(1)nm, β=108.509(1)° and Z=4; The Cu(Ⅰ) ion is chelated by a phen ligand and two aqua ligands in cis arrangement and assumes a C2 symmetric square-planar geometry with the CuN2O2 core. Eight Cu(phen)(H2O)2·ClO4 molecules are interconnected by strong hydrogen bonds between coordinated water molecules and uncoordinated perchlorate anions to form a molecular scale cavities along c axis. The bond distances of Cu-N and Cu-O are 0.2003(4)nm and 0.1973(3)nm, respectively. CCDC: 197600. 相似文献
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在醇溶剂中合成了2个铜配合物[Cu(Ⅱ)(phen)2Br]2[Cu(Ⅰ)4Br6](1)和[Cu(Ⅱ)(phen)2Br]Br·CH3OH(2)(phen=菲咯啉),并采用红外光谱、元素分析、热重和X射线单晶衍射对其进行了分析。1是Cu(Ⅰ)-Cu(Ⅱ)混价态化合物,并通过π-π作用和C-H…Br氢键作用形成了一个超分子网络结构。该化合物的结构单元包括2个[Cu(Ⅱ)(phen)2Br]+阳离子和1个[Cu(Ⅰ)4Br6]2-四核阴离子;阴离子中的4个铜原子组成四面体结构,而6个溴原子分别沿铜四面体的6个边桥联铜原子,形成八面体结构。2由[Cu(Ⅱ)(phen)2Br]+、Br-和CH3OH组成,并通过π-π作用也形成了一个超分子网络结构。当它们催化甲醇氧化羰基化合成碳酸二甲酯(DMC)时,2仅显示了5.9的DMC转化数,而1中的[Cu(Ⅰ)4Br6]2-阴离子能为甲醇的氧化羰基化反应提供适宜的合成环境,DMC的转化数达到54.7。 相似文献
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在醇溶剂中合成了2个铜配合物[Cu(Ⅱ)(phen)2Br]2[Cu(Ⅰ)4Br6](1)和[Cu(Ⅱ)(phen)2Br]Br·CH3OH(2)(phen=菲咯啉),并采用红外光谱、元素分析、热重和X射线单晶衍射对其进行了分析。1是Cu(Ⅰ)-Cu(Ⅱ)混价态化合物,并通过π-π作用和C-H…Br氢键作用形成了一个超分子网络结构。该化合物的结构单元包括2个[Cu(Ⅱ)(phen)2Br]+阳离子和1个[Cu(Ⅰ)4Br6]2-四核阴离子;阴离子中的4个铜原子组成四面体结构,而6个溴原子分别沿铜四面体的6个边桥联铜原子,形成八面体结构。2由[Cu(Ⅱ)(phen)2Br]+、Br-和CH3OH组成,并通过π-π作用也形成了一个超分子网络结构。当它们催化甲醇氧化羰基化合成碳酸二甲酯(DMC)时,2仅显示了5.9的DMC转化数,而1中的[Cu(Ⅰ)4Br6]2-阴离子能为甲醇的氧化羰基化反应提供适宜的合成环境,DMC的转化数达到54.7。 相似文献
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Dr. Zhen‐Tao Yu Yong‐Jun Yuan Jian‐Guang Cai Prof. Dr. Zhi‐Gang Zou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1303-1310
Two new charge‐neutral iridium complexes, [Ir(tfm‐ppy)2(N,N′‐diisopropyl‐benzamidinate)] ( 1 ) and [Ir(tfm‐ppy)2(N,N′‐diisopropyl‐4‐diethylamino‐3,5‐dimethyl‐benzamidinate)] ( 2 ) (tfm‐ppy=4‐trifluoromethyl‐2‐phenylpyridine) containing an amidinate ligand and two phenylpyridine ligands were designed and characterised. The photophysical properties, electrochemical behaviours and emission quenching properties of these species were investigated. In concert with the cobalt catalyst [Co(bpy)3]2+, members of this new class of iridium complexes enable the photocatalytic generation of hydrogen from mixed aqueous solutions via an oxidative quenching pathway and display long‐term photostability under constant illumination over 72 h; one of these species achieved a relatively high turnover number of 1880 during this time period. In the case of complex 1 , the three‐component homogeneous photocatalytic system proved to be more efficient than a related system containing a charged complex, [Ir(tfm‐ppy)2(dtb‐bpy)]+ ( 3 , dtb‐bpy=4,4′‐di‐tert‐butyl‐2,2′‐dipyridyl). In combination with a rhodium complex as a water reduction catalyst, the performances of the systems using both complexes were also evaluated, and these systems exhibited a more efficient catalytic propensity for water splitting than did the cobalt‐based systems that have been studied previously. 相似文献
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Ping Wang Guangchao Liang Noah Smith Kyra Hill Bruno Donnadieu Charles Edwin Webster Xuan Zhao 《Angewandte Chemie (International ed. in English)》2020,59(31):12694-12697
To explore the structure–function relationships of cobalt complexes in the catalytic hydrogen evolution reaction (HER), we studied the substitution of a tertiary amine with a softer pyridine group and the inclusion of a conjugated bpy unit in a Co complex with a new pentadentate ligand, 6‐[6‐(1,1‐di‐pyridin‐2‐yl‐ethyl)‐pyridin‐2‐ylmethyl]‐[2,2′]bipyridinyl (Py3Me‐Bpy). These modifications resulted in significantly improved stability and activity in both electro‐ and photocatalytic HER in neutral water. [Co(Py3Me‐Bpy)(OH2)](PF6)2 catalyzes the electrolytic HER at ?1.3 V (vs. SHE) for 20 hours with a turnover number (TON) of 266 300, and photolytic HER for two days with a TON of 15 000 in pH 7 aqueous solutions. The softer ligand scaffold possibly provides increased stability towards the intermediate CoI species. DFT calculations demonstrate that HER occurs through a general electron transfer/proton transfer/electron transfer/proton transfer pathway, with H2 released from the protonation of CoII?H species. 相似文献