吡啶基酞菁Ru配合物电子结构和光谱性质计算

doi:10.6023/A14040310

化学学报 ›› 2014, Vol. 72 ›› Issue (6): 697-703.DOI: 10.6023/A14040310 上一篇下一篇

研究论文

吡啶基酞菁Ru配合物电子结构和光谱性质计算

张明晶^a, 潘清江^a, 郭元茹^b, 张红星^c

a. 黑龙江大学化学化工与材料学院功能无机材料化学省部共建教育部重点实验室哈尔滨 150080;
b. 东北林业大学材料科学与工程学院生物质材料科学与技术教育部重点实验室哈尔滨 150040;
c. 吉林大学理论化学研究所理论化学计算国家重点实验室长春 130023

投稿日期:2014-04-22 发布日期:2014-05-14
通讯作者: 潘清江，郭元茹 E-mail:panqjitc@163.com;guoyrnefu@163.com
基金资助:
项目受国家自然科学基金（No.21273063）、教育部新世纪优秀人才支持计划（No.NCET-11-0958）和黑龙江省留学回国人员科技项目择优资助.

Electronic Structures and Spectroscopy of Pyridyl Ru-phthalocyanine Photosensitizers

Zhang Mingjing^a, Pan Qingjiang^a, Guo Yuanru^b, Zhang Hongxing^c

a. Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080;
b. Key Laboratory of Bio-based Material Science & Technology of Education Ministry, College of Material Science and Engineering, Northeast Forestry University, Harbin 150040;
c. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023

Received:2014-04-22 Published:2014-05-14
Supported by:
Project supported by National Natural Science Foundation of China (No.21273063), Program for New Century Excellent Talents in University (No.NCET-11-0958) and the Foundation of Heilongjiang Province for the Returned Overseas Chinese Scholars.

文章分享

摘要/Abstract

使用DFT和TD-DFT方法研究配合物[PcRu（RPy）（Py-COOH）]（Pc为酞菁；Py为吡啶；R分别代表COOH，CN，H，Me和OMe）以及它们的单、双电子氧化衍生物的电子结构和吸收光谱，分析表明中性配合物分子要比其氧化态更适合做染料.计算配合物在350 nm处有一个较强的Soret高能吸收带，而在600 nm的Q带吸收相对较弱.这些电子光谱被指认为酞菁环内的π→π^*跃迁和Ru→Py-COOH电荷转移.由于染料是通过轴向吡啶上的羧酸与半导体光阳极相联接，所以配合物的π→π^*跃迁对随后的电子注入没有贡献；加之该类配合物在400～580 nm可见光区无吸收，解释了该类配合物染料敏化太阳能电池光电转换效率低的原因.

关键词: 酞菁Ru光敏染料, 单、双电子氧化态, 电子光谱, 含时密度泛函理论

It is well known that photosensitizers play a vital role in the dye-sensitized solar cells (DSSCs).Understanding of their structures and photophysical properties is necessary to enhance the photoelectric conversion efficiency of DSSCs.In this work, a series of sensitizers [PcRu(RPy)(Py-COOH)] (Pc=phthalocyanine, Py=pyridine, R=COOH, CN, H, Me and OMe) as well as their one- and two-electron oxidized derivatives have been investigated using density functional theory (DFT) and time-dependent DFT.Their structural and spectroscopic properties were addressed.Full optimization demonstrates the ruthenium center exhibits octahedral geometry with six nitrogen donors.One- and two-electron oxidation slightly shortens equatorial Ru-N bond lengths relative to neutral dyes, but lengthens their axial ones.The experimentally known RuPc-1 has been calculated to evaluate performance of various functionals, basis sets, computational models of solvent effect and solvent sorts.And the TD-BLYP/SDD/PCM/Ethanol approach was used for spectral calculation in the present work.The comparison among calculated absorption spectra reveals that the neutral complexes are more suitable for photosensitizers in dye-sensitized solar cells than their oxidized derivatives.Neutral dyes were calculated to display a strong Soret absorption peak at 350 nm and a relatively weak Q band at 600 nm.They were assigned as intra-phthalocyanine π→π^* transition and Ru→Py-COOH metal-to-ligand charge transfer.As these dyes anchor to semiconductor photoanode by the carboxyl of axial pyridyl group, their π→π^* transition has no contribution to the subsequent electron injection.Further association with above ruthenium dyes missing absorption between 400～580 nm in visible region elucidates why DSSCs sensitized by them have such a low overall conversion efficiency of photo to electricity.Building on the present results, it is suggested to fabricate a sensitizer like [((COOH)_n-(Pc))Ru(L)₂], where anchoring carboxylic acids are bonded to equatorial Pc macrocycle and strong electron-donating groups are axially introduced.With this arrangement, Ru center, donating L groups and Pc macrocycle (high-lying π occupied orbitals) all serve as electron donors, while Pc ligand (low-lying π^* unfilled orbitals) and peripheral carboxylic substituents behave as electron-accepting reservoir.This in-progress work is anticipated to design dyes that improve the conversion efficiency of DSSCs.

Key words: Ru-phthalocyanine sensitizer, one- and two-electron oxidation, electronic spectrum, time-dependent density functional theory (TD-DFT)

引用此文

张明晶, 潘清江, 郭元茹, 张红星. 吡啶基酞菁Ru配合物电子结构和光谱性质计算[J]. 化学学报, 2014, 72(6): 697-703.

Zhang Mingjing, Pan Qingjiang, Guo Yuanru, Zhang Hongxing. Electronic Structures and Spectroscopy of Pyridyl Ru-phthalocyanine Photosensitizers[J]. Acta Chimica Sinica, 2014, 72(6): 697-703.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] O’Regan, B.; Grfitzeli, M.Nature 1991, 353, 24.
[2] Grätzel, M.Nature 2001, 414(6861), 338.
[3] Grätzel, M.J.Photochem.Photobiol.C 2003, 4(2), 145.
[4] Yella, A.; Lee, H.W.; Tsao, H.N.; Yi, C.; Chandiran, A.K.; Nazeeruddin, M.K.; Guang Diau, E.W.; Zakeeruddin, S.M.; Grätzel, M.Science 2011, 334(6056), 629.
[5] Wang, J.W.; Li, Y.; Xu, Y.L.; Li, Y.; Shen, K.H.Acta Chim.Sinica 2012, 70(11), 1278.(王纪伟, 李莹, 徐艳玲, 李杨, 申凯华, 化学学报, 2012, 70(11), 1278)
[6] Tang, X.; Wang, Y.X.Acta Chim.Sinica 2012, 71(02), 193.(唐笑, 汪禹汛, 化学学报, 2012, 71(02), 193.)
[7] Liang, M.; Xu, Y.J.; Wang, X.D.; Liu, X.J.; Sun, Z.; Xue, G.Acta Chim.Sinica 2011, 69(18), 2092.(梁茂, 徐英军, 王旭达, 刘秀杰, 孙喆, 薛松, 化学学报, 2011, 69(18), 2092.)
[8] He, J.J.; Chen, S.X.; Wang, T.T.; Zeng, H.P.Chin.J.Org.Chem.2012, 32, 472.(何俊杰, 陈舒欣, 王婷婷, 曾和平, 有机化学, 2012, 32, 472.)
[9] Zhang, Z.Y.; Han, J.L.; Li, X.; Cai, S.Y.; Su, J.H.Chin.J.Chem.2012, 30(12), 2779.
[10] Kuang, D.; Klein, C.; Ito, S.; Moser, J.E.; Humphry-Baker, R.; Zakeeruddin, S.M., Grätzel, M.Adv.Funct.Mater.2007, 17(1), 154.
[11] Chen, C.Y.; Chen, J.G.; Wu, S.J.; Li, J.Y.; Wu, C.G.; Ho, K.C.Angew.Chem., Int.Ed.2008, 47(38), 7342.
[12] Gao, F.; Wang, Y.; Shi, D.; Zhang, J.; Wang, M.K.; Jing, X.Y.; Humphry-Baker, R.; Wang, P.; Zakeeruddin, S.M., Grätzel, M.J.Am.Chem.Soc.2008, 130(32), 10720.
[13] Nazeeruddin, M.K.; Kay, A.; Rodicio, I.; Humphry-Baker, R.; Müller, E.; Liska, P.; Vlachopoulos, N.; Grätzel, M.J.Am.Chem.Soc.1993, 115(14), 6382.
[14] Rawling, T.; McDonagh, A.M.; Colbran, S.B.Inorg.Chim.Acta 2008, 361(1), 49.
[15] Rodriguez-Morgade, M.S.; Plonska-Brzezinska, M.E.; Athans, A.J.; Carbonell, E.; de Miguel, G.; Guldi, D.M.; Echegoyen, L.; Torres, T.J.Am.Chem.Soc.2009, 131(30), 10484.
[16] Rodríguez-Morgade, M.S.; Planells, M.; Torres, T.; Ballester, P.; Palomares, E.J.Mater.Chem.2008, 18(2), 176.
[17] Fischer, M.K.R.; López-Duarte, I.; Wienk, M.M.; Martínez-Díaz, M.V.; Janssen, R.A.J.; Bäuerle, P.; Torres, T.J.Am.Chem.Soc.2009, 131(24), 8669.
[18] Zhang, T.L.; Yan, J.M.Acta Chim.Sinica 2000, 58(8), 981.(张天莉, 严继民, 化学学报, 2000, 58(8), 981.)
[19] Morandeira, A.; López-Duarte, I.; O'Regan, B.; Martinez-Diaz, M.V.; Forneli, A.; Palomares, E.; Torres, T.; Durrant, J.R.J.Mater.Chem.2009, 19(28), 5016.
[20] O'Regan, B.C.; López-Duarte, I.; Martínez-Díaz, M.V.; Forneli, A.; Albero, J.; Morandeira, A.; Palomares, E.; Torres, T.; Durrant, J.R.J.Am.Chem.Soc.2008, 130(10), 2906.
[21] Morandeira, A.; López-Duarte, I.; Martínez-Díaz, M.V.; O'Regan, B.; Shuttle, C.; Haji-Zainulabidin, N.A.; Torres, T.; Palomares, E.; Durrant, J.R.J.Am.Chem.Soc.2007, 129(30), 9250.
[22] Reddy, P.Y.; Giribabu, L.; Lyness, C.; Snaith, H.J.; Vijaykumar, C.; Chandrasekharam, M.; Lakshmikantam, M.; Yum, J.H.; Kalyanasundaram, K.; Grätzel, M.Angew.Chem., Int.Ed.2007, 46(3), 373.
[23] Laikov, D.N.Chem.Phys.Lett.1997, 281(1), 151.
[24] Laikov, D.; Ustynyuk, Y.A.Russ.Chem.Bull.2005, 54(3), 820.
[25] Laikov, D.N.J.Comput.Chem.2007, 28(3), 698.
[26] Frisch, M.J.E.A.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G.A.Gaussian 09, Revision A.02, Gaussian, Inc, Wallingford, CT, 2009, 200.
[27] Rawling, T.; McDonagh, A.Coord.Chem.Rev.2007, 251(9), 1128.
[28] Sievertsen, S.; Weidemann, M.; Hueckstaedt, H.; Homborg, H.J.Porphyrins Phthalocyanines 1997, 1(04), 379.
[29] Listorti, A.; López-Duarte, I.; Martinez-Diaz, M.V.; Torres, T.; DosSantos, T.; Barnes, P.R.F.; Durrant, J.R.Energy Environ.Sci.2010, 3(10), 1573.
[30] Yanagisawa, M.; Korodi, F.; He, J.; Sun, L.; Sundström, V.; Åkermark, B.J.Porphyrins Phthalocyanines 2002, 6(03), 217.
[31] Yanagisawa, M.; Korodi, F.; Bergquist, J.; Holmberg, A.; Hagfeldt, A.; Åkermark, B.; Sun, L.C.J.Porphyrins Phthalocyanines 2004, 8(10), 1228.

吡啶基酞菁Ru配合物电子结构和光谱性质计算

Electronic Structures and Spectroscopy of Pyridyl Ru-phthalocyanine Photosensitizers

PDF

可视化

被引次数

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	刘艳, 孙世玲, 孙秀欣, 刘春光, 仇永清. C^N^NPt(II)及N^C^NPt(II)配合物二阶非线性光学性质的DFT研究[J]. 化学学报, 2011, 69(22): 2665-2672.
[2]	李雪, 孙世玲, 麻娜娜, 樊敏, 仇永清, 付强. 碳硼烷桥连噻吩化合物结构和二阶非线性光学系数的DFT计算[J]. 化学学报, 2011, 69(05): 523-528.
[3]	尹京花, 周子彦,王凌宇,吴学 . 2,2’-二甲基-4,4’-联噻唑与CHCl3分子间相互作用的理论研究[J]. 化学学报, 2009, 67(9): 923-928.
[4]	蔡静, 曾薇, 李权, 骆开均, 赵可清. 8-羟基喹啉过渡金属配合物电子光谱和二阶非线性光学性质的 DFT研究[J]. 化学学报, 2009, 67(20): 2301-2308.
[5]	仇毅翔,李佳,王曙光. 双核钯配合物Pd₂L₂和Pd₂L₂X₂ (L＝Me₂PCH₂PMe₂; X＝F, Cl, Br, I, H)的量子化学理论研究[J]. 化学学报, 2009, 67(14): 1585-1590.
[6]	陈俊蓉徐布一蔡静李权骆开均赵可清. 含长链β-二酮环金属铂配合物的电子光谱和二阶非线性光学性质的理论研究[J]. 化学学报, 2008, 66(13): 1513-1517.
[7]	尹京花,连慧琴, 周子彦, 赵继阳, 吴学^{. 6-羟基-5,12-萘并萘醌及其CH₃, C₆H₅取代衍生物的光致变色理论研究[J]. 化学学报, 2007, 65(24): 2821-2826.}
[8]	李小兵,王学业,禹新良,高进伟,朱卫国. 8-巯基喹啉阴离子的锌配合物及其衍生物的电子光谱性质的含时密度泛函理论研究[J]. 化学学报, 2006, 64(3): 208-212.
[9]	潘荧, 刘彩萍, 曾宝珊, 李巧红, 吴克琛. 一类五核平面开口型过渡金属原子簇电子吸收光谱和二阶非线性光学性质的TDDFT研究[J]. 化学学报, 2006, 64(20): 2039-2045.
[10]	仇毅翔, 王曙光. 金属四重键化合物M₂X₄(PMe₃)₄ (M＝Cr, Mo, W; X＝F, Cl, Br, I)结构和电子光谱的密度泛函理论研究[J]. 化学学报, 2006, 64(17): 1793-1798.
[11]	张明昕, 吴克琛, 莽朝永. 三核金配合物分子间Au-Au相互作用及其发光性质的含时密度泛函理论研究[J]. 化学学报, 2006, 64(16): 1681-1687.
[12]	仇毅翔,王曙光. Au(II)化合物[Au(CH₂)₂PH₂]₂X₂ (X＝F, Cl, Br, I)的量子化学理论研究[J]. 化学学报, 2006, 64(14): 1416-1422.
[13]	尹起范,朱玉兰,曹丽,阚玉和, 周建峰,南京熙,苏忠民. 2-(2,5-二羟基苯基)-5-甲基-2,5-二氢吡咯并[3,4]富勒烯的合成和电子光谱的理论研究[J]. 化学学报, 2005, 63(20): 1866-1870.
[14]	张敬来,王连宾,吴文鹏,曹泽星^{. 线性BC_2nB (n＝1～12)的结构特征和电子光谱的理论研究[J]. 化学学报, 2005, 63(2): 131-137.}
[15]	阚玉和,朱玉兰,侯丽梅,苏忠民. 含氯不对称配体8-羟基喹啉铝配合物电子和光谱性质的TDDFT研究[J]. 化学学报, 2005, 63(14): 1263-1268.