Effect of substituents and central metal ions on electronic structure and catalytic activity of porphyrins

doi:10.3969/j.issn.0438-1157.2013.z1.013

CIESC Journal ›› 2013, Vol. 64 ›› Issue (S1): 88-97.DOI: 10.3969/j.issn.0438-1157.2013.z1.013

Previous Articles Next Articles

Effect of substituents and central metal ions on electronic structure and catalytic activity of porphyrins

CAO Meijuan, YU Yanmin, FU Haiyan, SHE Yuanbin

1. Institute of Green Chemistry and Fine Chemicals, College of Environmental & Energy Engineering, Beijing University of Technology, Beijing 100124, China;
2. Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, College of Chemistry and Materials Science, South-Central University for Nationalities, Wuhan 430074, Hubei, China;
3. College of Pharmacy, South-Central University for Nationalities, Wuhan 430074, Hubei, China

Received:2013-11-01 Revised:2013-11-10 Online:2013-12-30 Published:2013-12-30
Supported by:
supported by the National Natural Science Fundation of China (21276006, 21036009, 21076004, 21205145, 21376010), the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality (PHR 201107104) and the Talents Fund of South-Central University for Nationalities (YZZ12002, XTZ13002).

取代基及中心金属离子对卟啉电子结构及催化活性的影响

1. 北京工业大学环能学院绿色化学与精细化工研究所, 北京 100124;
2. 中南民族大学化学与材料科学学院催化材料科学国家民委-教育部共建暨湖北省重点实验室, 湖北武汉 430074;
3. 中南民族大学药学院, 湖北武汉 430074

通讯作者: 佘远斌
作者简介:曹梅娟(1980—)，女，博士研究生。
基金资助:
国家自然科学基金项目(21276006, 21036009, 21076004, 21205145, 21376010)；北京市属市管高等学校人才强教计划项目(PHR 201107104)；中南民族大学引进人才基金和中南民族大学团队项目 (YZZ12002, XTZ13002)。

Abstract

Abstract: How to adjust the microstructure, macroproperties and function of prophyrins by tuning the substituents and central metal ions species has been the key and the challenge problem for designing the high activity and selectivity catalysts. It can provide important theoretical foundation for the accurate designing of metalloporphyrin catalysts to study the effects of the substituents and central metal ions on the electronic structure properties of porphyrins. In order to understand the relationship between microstructure and macro catalytic efficiency of porphyrins in essence, the electronic structures of metalloporphyrins with different substituents (—OCH₃，—CH₃，—H，—NO₂) and different central metal ions (Mn，Fe，Co，Cu，Zn) were investigated using computational chemistry method based on density functional. The results indicated that the electron-withdrawing substituent (—NO₂) lowered the levels of the highest occupied orbitals (HOMO) and lowest unoccupied orbital (LUMO) of metalloporphyrins. Whereas the electron-donating substitutes increased the levels of the HOMO and LUMO of metalloporphyrins. The central metal ions have an effect on the distribution of frontier molecular orbital. The frontier molecular orbitals of variant valence metalloporphyrins (Mn，Fe，Co) were mainly composed of 3 d orbital of metal ions, which facilitated the activation of dioxygen. The frontier molecular orbitals of invariant valence metalloporphyrins (Cu，Zn) were composed of large π bond from porphyrin ligands. The electrons could transport fluently in the large π bond, therefore the invariant valence metalloporphyrins also have the high activity. Fukui function suggested that the active sites of variant valence metalloporphyrins located on the central metal ions. Whereas the active sites of invariant valence metalloporphyrins might locate on the porphyrin ligands.

Key words: porphyrin, computational chemistry, electronic structure, catalysis, activity

摘要： 通过调变取代基及中心金属离子种类调控金属卟啉的微观分子结构和宏观性质与功能是设计高活性、高选择性的金属卟啉催化剂的关键及富有挑战性的课题。取代基和中心金属离子对金属卟啉电子结构性质的影响研究可为金属卟啉催化剂的精确设计提供重要的理论依据。采用基于密度泛函理论计算化学方法系统地研究了不同取代基(—OCH₃、—CH₃、—H、—NO₂)及中心金属离子(Mn、Fe、Co、Cu、Zn)对卟啉电子结构性质的影响，试图从本质上理解金属卟啉微观结构和宏观催化性能的关系。结果表明，吸电子基—NO₂总是降低金属卟啉的最高占据轨道(HOMO)和最低未占据轨道(LUMO)能级，而供电子基—CH₃和—OCH₃总是升高金属卟啉的HOMO和LUMO能级。变价金属(Mn、Fe、Co)卟啉的前线分子轨道主要由金属离子的3 d轨道组成，有利于活化分子氧。不变价金属(Cu、Zn)卟啉的前线分子轨道的成分为卟啉配体形成的大π键，电子流动性好，故不变价金属也有较高的催化活性。Fukui函数分析表明变价金属卟啉的活性中心位于中心金属离子，而不变价金属卟啉的活性中心可能在卟啉配体上。

关键词: 卟啉, 计算化学, 电子结构, 催化, 活性

CLC Number:

TQ426.7

CAO Meijuan, YU Yanmin, FU Haiyan, SHE Yuanbin. Effect of substituents and central metal ions on electronic structure and catalytic activity of porphyrins[J]. CIESC Journal, 2013, 64(S1): 88-97.

曹梅娟, 于艳敏, 付海燕, 佘远斌. 取代基及中心金属离子对卟啉电子结构及催化活性的影响[J]. 化工学报, 2013, 64(S1): 88-97.

References 37

[1]	Mansuy D. A brief history of the contribution of metalloporphyrin models to cytochrome P450 chemistry and oxidation catalysis[J]. Comptes Rendus Chimie, 2007, 10(4): 392-413
[2]	Nakagaki S, Ferreira G K B, Ucoski G M, Castro K A D F. Chemical reactions catalyzed by metalloporphyrin-based metal-organic frameworks[J]. Molecules, 2013, 18(6): 7279-7308
[3]	Campestrini S, Meunier B. Olefin epoxidation and alkane hydroxylation catalyzed by robust sulfonated manganese and iron porphyrins supported on cationic ion-exchange resins[J]. Inorganic Chemistry, 1992, 31(11): 1999-2006
[4]	Lyons J E, Ellis Jr P E. Selective low temperature hydroxylation of isobutane by molecular oxygen catalyzed by an iron perhaloporphyrin complex[J]. Catalysis Letters, 1991, 8(1): 45-51
[5]	Chen H L, Ellis Jr P E, Wijesekera T, Hagan T E, Groh S E, Lyons J E, Ridge D P. Correlation between gas-phase electron affinities, electrode potentials, and catalytic activities of halogenated metalloporphyrins[J]. Journal of the American Chemical Society, 1994, 116(3): 1086-1089
[6]	Lyons J E, Ellis P E, Myers H K. Halogenated metalloporphyrin complexes as catalysts for selective reactions of acyclic alkanes with molecular oxygen[J]. Journal of Catalysis, 1995, 155(1): 59-73
[7]	Lyaskovskyy V，Suarez AI O，Lu Hongjian. Mechanism of cobalt (Ⅱ) porphyrin-catalyzed C—H amination with organic azides: radical nature and H-atom abstraction ability of the key cobalt(Ⅲ)-nitrene intermediates[J].Journal of the American Chemical Society, 2011, 133(31): 12264-12273
[8]	Lu Hongjian，Zhang X Peter. Catalytic C—H functionalization by metalloporphyrins: recent developments and future directions[J]. Chemical Society Reviews, 2011, 40(4): 1899-1909
[9]	Liu Wei, Huang Xiongyi, Cheng M J, Nielsen R J, Goddard Ⅲ W A, Groves J T. Oxidative aliphatic C—H fluorination with fluoride ion catalyzed by a manganese porphyrin[J]. Science, 2012, 337(6100): 1322-1325
[10]	Zhou Xiantai，Tang Qinghua，Ji Hongbing. Remarkable enhancement of aerobic epoxidation reactivity for olefins catalyzed by μ-oxo-bisiron (Ⅲ) porphyrins under ambient conditions[J]. Tetrahedron Letters, 2009, 50(47): 6601-6605
[11]	Zhou Xiantai, Ji Hongbing, Yuan Qiulan. Baeyer-Villiger oxidation of ketones catalyzed by iron (Ⅲ) meso-tetraphenylporphyrin chloride in the presence of molecular oxygen[J]. Journal of Porphyrins and Phthalocyanines, 2008, 12(2): 94-100
[12]	Zhou Xiantai, Yuan Qiulan, Ji Hongbin. Highly efficient aerobic oxidation of oximes to carbonyl compounds catalyzed by metalloporphyrins in the presence of benzaldehyde[J]. Tetrahedron Letters, 2010, 51(4): 613-617
[13]	She Yuanbin(佘远斌)，Wang Lanzhi(王兰芝)，Song Xufeng(宋旭锋). Synthesis and QSAR of metal porphyrin biomimetic catalysts and their application in oxidation of hydrocarbons.[J] Fine Chemicals (精细化工), 2005, 22(6): 401-408
[14]	Sun Zhicheng, She Yuanbin, Zhou Xiantai. Synthesis, characterization and spectral properties of substituted tetraphenylporphyrin iron chloride complexes[J]. Molecules, 2011, 16(4): 2960-2970
[15]	She Yuabin, Wang Weijie, Li Guojun. Oxidation of p/o-hydroxybenzaldehydes catalyzed by metalloporphyrins with molecular oxygen[J]. Chinese Journal of Chemical Engineering, 2012, 20(2): 262-266
[16]	Guo Cancheng，Liu Xiaoqin, Liu Yang, Liu Qiang, Chu Mingfu, Zhang Xiaobing. Studies of simple μ-oxo-bisiron (Ⅲ) porphyrin as catalyst of cyclohexane oxidation with air in absence of cocatalysts or coreductants[J]. Journal of Molecular Catalysis A: Chemical, 2003, 192(1): 289-294
[17]	Guo Cancheng, Huang Gang, Zhang Xiaoqing, Guo Dongcai. Catalysis of chitosan-supported iron tetraphenylporphyrin for aerobic oxidation of cyclohexane in absence of reductants and solvents[J]. Applied Catalysis A: General, 2003, 247(2): 261-267
[18]	Liao Yuting(廖玉婷)，Zhang Yulei(张宇蕾)，Ma Siyu(马思渝). A theoretical study on the substituent effect of porphine symmetry[J]. Journal of Beijing Normal University:Natural Science(北京师范大学学报:自然科学版), 2005(6): 608-612
[19]	Fa Huanbao(法焕宝)，Wang Xingqiao(王杏乔). Electrochemical properties of porphyrins and transition metalloporphyrins[J]. Journal of Jilin University:Science Edition(吉林大学学报:理学版), 2007, 45(1): 107-110
[20]	Guo Cancheng(郭灿城)，Zhang Shang(张尚)，Lei Yuwu(雷裕武). Study on the substituent effects of the oxidation of mono-and bisporphinatoiron(Ⅲ) with Phio[J]. Acta Chimica Sinica(化学学报), 1993, 51(9): 928-932
[21]	Yang Weijun(阳卫军)，Guo Canchen(郭灿城)，Mao Yanli(毛彦利). Relationship between electronical behavior of metalloporphyrins and their catalytic performance for α-pinenne oxidation[J]. Chinese Journal of Catalysis (催化学报), 2005, 26(5): 360-364
[22]	Ellis Jr P E, Lyons J E. Halogen substituent effects on the catalytic activity of iron porphyrin complexes for selective air-oxidation of alkanes in the liquid phase[J]. Catalysis Letters, 1989, 3(5/6): 389-397
[23]	Ghosh A. Substituent effects on valence ionization potentials of free base porphyrins: a local density functional study[J]. Journal of the American Chemical Society, 1995, 117(16): 4691-4699
[24]	Nifiatis F, Athas J C, Gunaratne K D, Gunararne K D D, Gurung Y, Monette K M, Shivokevich P J. Substituent effects of porphyrin on singlet oxygen generation quantum yields[J]. Open Spectroscopy Journal, 2011, 5: 1-12
[25]	Zhang Lijuan，Qi Dongdong，Zhao Luyang, Bian Yongzhong, Li Wenjun. Substituent effects on the structure-property relationship of unsymmetrical methyloxy and methoxycarbonyl phthalocyanines: DFT and TDDFT theoretical studies[J]. Journal of Molecular Graphics and Modelling, 2012, 35: 57-65
[26]	Wei Lu, She Yuanbin, Yu Yanmin, Yao Xiaoqian, Zhang Suojiang. Substituent effects on geometric and electronic properties of iron tetraphenylporphyrin: a DFT investigation[J]. Journal of Molecular Modelling, 2012, 18(6): 2483-2491
[27]	Wang Lanzhi(王兰芝), She Yuanbin(佘远斌), Zhong Rugang(钟儒刚). Relationship between structure and catalytic activity of chloro-iron tetraphenylporphyrin compounds[J]. Journal of Chemical Industry and Engineering (China) (化工学报), 2006, 57(6): 1339
[28]	Zhang Yanhui(张燕慧), She Yuanbin(佘远斌), Zhong Rugang(钟儒刚), Zhou Xiantai(周贤太), Ji Hongbing(纪红兵). Study on the correlation between molecular frontier orbital energy and catalytic activity of cobalt porphyrins[J]. Acta Chimica Sinica(化学学报), 2004, 62: 2228-2232
[29]	Yuan Ying, Ji Hongbing, Chen Yixia, Han Yong, Song Xufeng, She Yuanbin, Zhong Rugang. Oxidation of cyclohexane to adipic acid using Fe-porphyrin as a biomimetic catalyst[J]. Organic Process Research & Development, 2004, 8(3): 418-420
[30]	She Yuanbin(佘远斌), Luo Zhenhua(罗振华), Song Xufeng(宋旭锋), Duan Lili(段丽丽), Yun Yue(恽悦), Zhang Tianhui(张天慧). Novel green synthesis of o-nitrobenzaldehyde by oxidation of o-nitrotoluene with metal porphyrins as biomimetic catalysts[J]. Journal of Chemical Industry and Engineering (China) (化工学报) 2007, 58(11): 2782
[31]	Wang Mei, She Yuanbin, Zhou Xiantai, Ji Hongbing. Efficient solvent-free synthesis of chloropropene carbonate from the coupling reaction of CO2 and epichlorohydrin catalyzed by magnesium porphyrins as chlorophyll-like catalysts[J]. Chinese Journal of Chemical Engineering, 2011, 19(3): 446-451
[32]	Balanay M P, Lee S H, Yu S, Kim D H. Application of long-range-corrected density functional in metallated porphyrin analogues for dye-sensitized solar cells[J]. Notes, 2011, 32(2): 705
[33]	Asghari-Khiavi M, Safinejad F. Theoretical studies on metal porphyrin halides: geometrical parameters and nonlinear optical responses[J]. J. Molecular Modelling, 2010, 16(3): 499-503
[34]	Vogel E, Brring M, Fink J, Rosen D, Schmickler H, Lex J, Chan K W K, Wu Y D, Plattner D A, Nendel M, Houk K N. From porphyrin isomers to octapyrrolic “Figure Eight” macrocycles[J]. Angewandte Chemie International Edition in English, 1995, 34(22): 2511-2514
[35]	Becke A D. Density-functional exchange-energy approximation with correct asymptotic behavior[J]. Physics Review A, 1988, 38(6): 3098-3100
[36]	Lee C, Yang W, Parr R G. Development of the Colle-Salvetti conelation energy formula into a functional of the electron density[J]. Physics Review B, 1988, 37, 785-789
[37]	Zhao Wenbo(赵文伯), She Yuanbin(佘远斌), Wang Pan(王磐), Li Linsha(李林莎)， Zhang Yanhui(张燕慧). Aerobic oxidation of 4-nitroethylbenzene to 4-nitroacetophenone catalyzed by metalloporphyrins or compounding catalytic systems[J]. Journal of Beijing University of Technology(北京工业大学学报), 2012, 38, 773-777

Effect of substituents and central metal ions on electronic structure and catalytic activity of porphyrins

取代基及中心金属离子对卟啉电子结构及催化活性的影响

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References 37

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Yepin CHENG, Daqing HU, Yisha XU, Huayan LIU, Hanfeng LU, Guokai CUI. Application of ionic liquid-based deep eutectic solvents for CO₂ conversion [J]. CIESC Journal, 2023, 74(9): 3640-3653.
[2]	Minghao SONG, Fei ZHAO, Shuqing LIU, Guoxuan LI, Sheng YANG, Zhigang LEI. Multi-scale simulation and study of volatile phenols removal from simulated oil by ionic liquids [J]. CIESC Journal, 2023, 74(9): 3654-3664.
[3]	Erqi WANG, Shuzhou PENG, Zhen YANG, Yuanyuan DUAN. Evaluation of vapor-liquid equilibrium models for mixtures containing HFOs [J]. CIESC Journal, 2023, 74(8): 3216-3225.
[4]	Lingding MENG, Ruqing CHONG, Feixue SUN, Zihui MENG, Wenfang LIU. Immobilization of carbonic anhydrase on modified polyethylene membrane and silica [J]. CIESC Journal, 2023, 74(8): 3472-3484.
[5]	Yaxin CHEN, Hang YUAN, Guanzhang LIU, Lei MAO, Chun YANG, Ruifang ZHANG, Guangya ZHANG. Advances in enzyme self-immobilization mediated by protein nanocages [J]. CIESC Journal, 2023, 74(7): 2773-2782.
[6]	Xiaoling TANG, Jiarui WANG, Xuanye ZHU, Renchao ZHENG. Biosynthesis of chiral epichlorohydrin by halohydrin dehalogenase based on Pickering emulsion system [J]. CIESC Journal, 2023, 74(7): 2926-2934.
[7]	Xiaokun HE, Rui LIU, Yuan XUE, Ran ZUO. Review of gas phase and surface reactions in AlN MOCVD [J]. CIESC Journal, 2023, 74(7): 2800-2813.
[8]	Tan ZHANG, Guang LIU, Jinping LI, Yuhan SUN. Performance regulation strategies of Ru-based nitrogen reduction electrocatalysts [J]. CIESC Journal, 2023, 74(6): 2264-2280.
[9]	Lei MAO, Guanzhang LIU, Hang YUAN, Guangya ZHANG. Efficient preparation of carbon anhydrase nanoparticles capable of capturing CO₂ and their characteristics [J]. CIESC Journal, 2023, 74(6): 2589-2598.
[10]	Lixiang ZHU, Moye LUO, Xiaodong ZHANG, Tao LONG, Ran YU. Application of quinone profile method to indicate structure and activity of functional microbial community in trichloroethylene-contaminated soil [J]. CIESC Journal, 2023, 74(6): 2647-2654.
[11]	Chenxi LI, Yongfeng LIU, Lu ZHANG, Haifeng LIU, Jin’ou SONG, Xu HE. Quantum chemical analysis of n-heptane combustion mechanism under O₂/CO₂ atmosphere [J]. CIESC Journal, 2023, 74(5): 2157-2169.
[12]	Zijian WANG, Ming KE, Jiahan LI, Shuting LI, Jinru SUN, Yanbing TONG, Zhiping ZHAO, Jiaying LIU, Lu REN. Progress in preparation and application of short b-axis ZSM-5 molecular sieve [J]. CIESC Journal, 2023, 74(4): 1457-1473.
[13]	Tianhao BAI, Xiaowen WANG, Mengzi YANG, Xinwei DUAN, Jie MI, Mengmeng WU. Study on release and inhibition behavior of COS during high-temperature gas desulfurization process using Zn-based oxide derived from hydrotalcite [J]. CIESC Journal, 2023, 74(4): 1772-1780.
[14]	Yin XU, Jie CAI, Lu CHEN, Yu PENG, Fuzhen LIU, Hui ZHANG. Advances in heterogeneous visible light photocatalysis coupled with persulfate activation for water pollution control [J]. CIESC Journal, 2023, 74(3): 995-1009.
[15]	Runzhu LIU, Tiantian CHU, Xiaoa ZHANG, Chengzhong WANG, Junying ZHANG. Synthesis and properties of phenylene-containing α,ω-hydroxy-terminated fluorosilicone polymers [J]. CIESC Journal, 2023, 74(3): 1360-1369.