对称卟啉自组装敏化剂的合成及理论研究
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摘要
本文合成了Zn Pi-Zn PA(i=1～3)自组装卟啉,用核磁、质谱进行了相关的表征,并用密度泛函理论(DFT)从理论上研究了其在染料敏化太阳能电池中的光电行为。Zn Pi-Zn PA(i=1～3)的最高占有分子轨道(HOMO)主要分布在冠卟啉,最低非占有分子轨道(LUMO)主要分布在锚定卟啉,这表明它们是良好的敏化剂。
In this paper, Zn Pi-Zn PA(i=1～3) self-assembled porphyrins were synthesized and characterized by NMR and MS. Their photoelectric performance was theoretically studied by density functional theory(DFT) in dye-sensitized solar cells. The highest occupied molecular orbital(HOMO) of Zn Pi-Zn PA(i=1～3) is mainly distributed in crown porphyrins, and the lowest non-occupied molecular orbital(LUMO) is mainly distributed in anchored porphyrins, indicating that they are good sensitizers.
In this paper, Zn Pi-Zn PA(i=1～3) self-assembled porphyrins were synthesized and characterized by NMR and MS. Their photoelectric performance was theoretically studied by density functional theory(DFT) in dye-sensitized solar cells. The highest occupied molecular orbital(HOMO) of Zn Pi-Zn PA(i=1～3) is mainly distributed in crown porphyrins, and the lowest non-occupied molecular orbital(LUMO) is mainly distributed in anchored porphyrins, indicating that they are good sensitizers.
引文
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[2]Bisquert J,Cahen D,Hodes G,et al,Physical Chemical Principles of Photovoltaic Conversion with Nanoparticulate,Mesoporous Dye-Sensitized Solar Cells[J].The Journal of Physical Chemistry B,2004,108(24):8106-8118.
[3]Mathew S,Yella A,Gao P,et al,Dye-sensitized solar cells with 13%efficiency achieved through the molecular engineering of porphyrin sensitizers[J].Nature Chemistry,2014,6(3):242-247.
[4]Han F,Yang J,Zhe Y,et al,Study on a series of novel self-assembly supramolecular solar cells based on a double-layer structured chromophore of Zn-porphyrins[J].Dalton Transactions,2016,45(21):8862-8868.
[5]Zhang J X,Wu Y,Liu J C.Bilayer structured supramolecular light harvesting arrays based on zinc porphyrin coordination polymers for enhanced photocurrent generation in dye sensitized solar cells[J].Dalton Trans,2016,45:16283-16289.
[6]Gouterman M,Spectra of porphyrins[J].Journal of Molecular Spectroscopy,1961,6:138-163.
[7]FRICH M,TRUCKS G,SCHLEGELI HB,et al,Gaussian09[M].Gaussian,Inc.Wallingford,CT,2009.
[8]Becke A D.Density-functional exchange-energy approximation with correct asymptotic behavior[J].Physical Review A,1988,38(38):3098-3100.
[9]Hehre W J,Ditchfield R,Pople J A,Self-Consistent Molecular Orbital Methods.XII.Further Extensions of Gaussian-Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules[J].Journal of Chemical Physics,1972,56(5):2257-2261.