Design of Panchromatic Metalloporphyrin Sensitizers owning Multiple Types of Transitions including D--A and Singlet and Spin-Orbit Coupling Activated Triplet Metal-to-Anchor Charge Transfers for Dye-sensitized Solar Cells

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姓名

林慧絜(Hui-Jie Lin) 查詢紙本館藏

畢業系所

化學學系

論文名稱

(Design of Panchromatic Metalloporphyrin Sensitizers owning Multiple Types of Transitions including D--A and Singlet and Spin-Orbit Coupling Activated Triplet Metal-to-Anchor Charge Transfers for Dye-sensitized Solar Cells)

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摘要(中)

我們使用密度泛函理論（TD-DFT）與spin–orbit coupling effect（SOC effect）來模擬計算把YD2-o-C8作為骨架的porphyrin染料中心金屬Zn換成Ru和Os，使用Cl-或PPh(OMe)2連接中心金屬，成為六配位的porphyrins，研究染料的電子結構和吸收光譜。具有兩個Cl-配位的Ru-和Os-porphyrins在near IR / IR區域邊緣顯示出較弱的吸收，這在原始的YD2-o-C8染料中沒有觀察到的。在長波長邊緣有吸收是源自金屬到受體的電荷轉移(MACT)，並進一步由具有重的Ru和Os原子的SOC effect造成紅位移的現象。另一方面，使用PPh(OMe)2 作為ligands的染料在near IR區域不產生吸收，結果可得PPh(OMe)2 ligand能穩定修飾Ru-和Os-porphyrins的“ t2g”軌道。另外也觀察到PPh(OMe)2連接的porphyrins有SOC effect。這項研究表明，將Ru和Os重原子引入以Cl-作為ligands的porphyrins可以誘導在長波長吸收的金屬到受體的電荷轉移，並進一步增強SOC effect，使吸收紅位移。研究結果為設計長波長躍遷提供了一種新方法，同時又保留了原有的染料骨架。

摘要(英)

We investigate the electronic structures and absorption spectra for Ru- and
Os-porphyrins ligated with Cl− or PPh(OMe)2 using an Zn-based YD2-o-C8 skeleton
as well as YD2-o-C8 and YD2 dyes by time-dependent density functional theory
(TD-DFT) with spin–orbit coupling (SOC) interactions. The Ru- and Os-porphyrins
modified with two Cl− as ligands exhibit a weak absorption onset in the near IR/IR
region, which is not observed in that of original YD2-o-C8 dye. The long wavelength
absorption edge originates from the metal to acceptor charge transfer MACT and is
further red-shifted from SOC with heavy Ru and Os atoms. On the other hand, the
PPh(OMe)2 ligands stabilizing the “t2g” orbitals of the modified Ru- and
Os-porphyrins do not induce absorption in the near IR region. However, SOC is also
observed for PPh(OMe)2 ligated Ru- and Os-porphyrins. This study shows that the
introduction of heavy Ru and Os atoms into porphyrin skeleton with Cl- as ligands can
induce long wavelength metal-to-acceptor charge transfer and further enhance the
SOC, red-shifting the absorption. This result offers a new approach for designing long
wavelength transitions, while remaining the original dye framework.

關鍵字(中)

★ DSSC
★ porphyrin
★ Spin-Orbit Coupling
★ Metalloporphyrin

關鍵字(英)

論文目次

摘要 I
Abstract II
Contents III
List of Scheme IV
List of Figures IV
List of Tables VI
Chapter 1—Introduction 1
Chapter 2—Computational Methods 6
Chapter 3—Results and Discussion 9
3.1 Geometrical Parameters of Studied Molecules 9
3.2 Electronic Structure and Absorption Spectra of YD2 and YD2-o 11
3.3 Electronic Structure and Absorption Spectra of YD2-o-Ru-2Cl and YD2-o-Ru-2P 22
3.4 Electronic Structure and Absorption Spectra of YD2-o-Os-2Cl and YD2-o-Os-2Cl 37
Chapter 4—Conclusions 49
References 51
Supporting Information 54

參考文獻

1. (a) O′Regan, B.; Grätzel, M., A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature 1991, 353 (6346), 737-740; (b) Grätzel, M., Dye-sensitized solar cells. Journal of Photochemistry and Photobiology C: Photochemistry Reviews 2003, 4 (2), 145-153; (c) Ripolles-Sanchis, T.; Guo, B. C.; Wu, H. P.; Pan, T. Y.; Lee, H. W.; Raga, S. R.; Fabregat-Santiago, F.; Bisquert, J.; Yeh, C. Y.; Diau, E. W., Design and characterization of alkoxy-wrapped push-pull porphyrins for dye-sensitized solar cells. Chem. Commun. 2012, 48 (36), 4368-70; (d) Higashino, T.; Imahori, H., Porphyrins as excellent dyes for dye-sensitized solar cells: recent developments and insights. Dalton transactions 2015, 44 (2), 448-63; (e) Gong, J.; Sumathy, K.; Qiao, Q.; Zhou, Z., Review on dye-sensitized solar cells (DSSCs): Advanced techniques and research trends. Renewable and Sustainable Energy Reviews 2017, 68, 234-246.
2. Mishra, A.; Fischer, M. K.; Bauerle, P., Metal-free organic dyes for dye-sensitized solar cells: from structure: property relationships to design rules. Angew. Chem. Int. Ed. 2009, 48 (14), 2474-99.
3. Chen, C.-Y.; Wu, S.-J.; Wu, C.-G.; Chen, J.-G.; Ho, K.-C., A Ruthenium Complex with Superhigh Light-Harvesting Capacity for Dye-Sensitized Solar Cells. Angew. Chem. Int. Ed. 2006, 45 (35), 5822-5825.
4. Kinoshita, T.; Dy, J. T.; Uchida, S.; Kubo, T.; Segawa, H., Wideband dye-sensitized solar cells employing a phosphine-coordinated ruthenium sensitizer. Nat. Photon. 2013, 7 (7), 535-539.
5. (a) Nazeeruddin, M. K.; Pechy, P.; Renouard, T.; Zakeeruddin, S. M.; Humphry-Baker, R.; Comte, P.; Liska, P.; Cevey, L.; Costa, E.; Shklover, V.; Spiccia, L.; Deacon, G. B.; Bignozzi, C. A.; Gratzel, M., Engineering of efficient panchromatic sensitizers for nanocrystalline TiO(2)-based solar cells. J. Am. Chem. Soc. 2001, 123 (8), 1613-24; (b) Han, L.; Islam, A.; Chen, H.; Malapaka, C.; Chiranjeevi, B.; Zhang, S.; Yang, X.; Yanagida, M., High-efficiency dye-sensitized solar cell with a novel co-adsorbent. Energ Environ. Sci. 2012, 5 (3), 6057.
6. Fantacci, S.; Ronca, E.; De Angelis, F., Impact of Spin-Orbit Coupling on Photocurrent Generation in Ruthenium Dye-Sensitized Solar Cells. J Phys Chem Lett 2014, 5 (2), 375-80.
7. Juwita, R.; Lin, J.-Y.; Lin, S.-J.; Liu, Y.-C.; Wu, T.-Y.; Feng, Y.-M.; Chen, C.-Y.; Gavin Tsai, H.-H.; Wu, C.-G., Osmium sensitizer with enhanced spin–orbit coupling for panchromatic dye-sensitized solar cells. J. Mater. Chem. A 2020.
8. (a) Gouterman, M., Study of the Effects of Substitution on the Absorption Spectra of Porphin. J. Chem. Phys. 1959, 30 (5), 1139-1161; (b) Gibson, J. F.; Ingram, D. J. E., Location of Free Electrons in Porphin Ring Complexes. Nature 1956, 178 (4538), 871-872; (c) Jansen, G.; Noort, M., High resolution spectra of zinc porphin and magnesium porphin in a n-octane matrix at 4.2 K. Effect of the addition of ethanol and other solvents. Spectrochimica Acta Part A: Molecular Spectroscopy 1976, 32 (4), 747-753; (d) Hashimoto, T.; Choe, Y. K.; Nakano, H.; Hirao, K., Theoretical study of the Q and B bands of free-base, magnesium, and zinc porphyrins, and their derivatives. J. Phys. Chem. A 1999, 103 (12), 1894-1904.
9. (a) Wang, C.-L.; Chang, Y.-C.; Lan, C.-M.; Lo, C.-F.; Wei-Guang Diau, E.; Lin, C.-Y., Enhanced light harvesting with π-conjugated cyclic aromatic hydrocarbons for porphyrin-sensitized solar cells. Energ Environ. Sci. 2011, 4 (5), 1788; (b) Tang, Y.; Wang, Y.; Li, X.; Agren, H.; Zhu, W. H.; Xie, Y., Porphyrins Containing a Triphenylamine Donor and up to Eight Alkoxy Chains for Dye-Sensitized Solar Cells: A High Efficiency of 10.9%. ACS Appl Mater Interfaces 2015, 7 (50), 27976-85; (c) Chang, Y. C.; Wang, C. L.; Pan, T. Y.; Hong, S. H.; Lan, C. M.; Kuo, H. H.; Lo, C. F.; Hsu, H. Y.; Lin, C. Y.; Diau, E. W., A strategy to design highly efficient porphyrin sensitizers for dye-sensitized solar cells. Chem. Commun. 2011, 47 (31), 8910-2; (d) Chou, H. H.; Reddy, K. S.; Wu, H. P.; Guo, B. C.; Lee, H. W.; Diau, E. W.; Hsu, C. P.; Yeh, C. Y., Influence of Phenylethynylene of Push-Pull Zinc Porphyrins on the Photovoltaic Performance. ACS Appl Mater Interfaces 2016, 8 (5), 3418-27.
10. Yella, A.; Lee, H. W.; Tsao, H. N.; Yi, C.; Chandiran, A. K.; Nazeeruddin, M. K.; Diau, E. W.; Yeh, C. Y.; Zakeeruddin, S. M.; Gratzel, M., Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency. Science 2011, 334 (6056), 629-34.
11. Bessho, T.; Zakeeruddin, S. M.; Yeh, C. Y.; Diau, E. W.; Gratzel, M., Highly efficient mesoscopic dye-sensitized solar cells based on donor-acceptor-substituted porphyrins. Angew. Chem. Int. Ed. 2010, 49 (37), 6646-9.
12. (a) Shalabi, A. S.; Abdel Aal, S.; El Mahdy, A. M., The effect of ruthenium on the performance of porphyrin dye and porphyrin–fullerene dyad solar cells predicted by DFT and TD-DFT calculations. Molecular Simulation 2013, 39 (9), 689-699; (b) Ladomenou, K.; Nikolaou, V.; Charalambidis, G.; Sharma, G. D.; Coutsolelos, A. G., Ru(II) porphyrins as sensitizers for DSSCs: Axial vs. peripheral carboxylate anchoring group. J. Porphyrins Phthalocyanines 2019, 23 (07n08), 870-880; (c) Che, C.-M.; Huang, J.-S., Ruthenium and osmium porphyrin carbene complexes: synthesis, structure, and connection to the metal-mediated cyclopropanation of alkenes. Coord. Chem. Rev. 2002, 231 (1-2), 151-164; (d) Berkessel, A.; Erturk, E.; Kaiser, P.; Klein, A.; Kowalczyk, R. M.; Sarkar, B., On the redox states of ruthenium porphyrin oxidation catalysts. Dalton transactions 2007, (31), 3427-34; (e) Antipas, A.; Buchler, J. W.; Gouterman, M.; Smith, P. D., Porphyrins. 36. Synthesis and optical and electronic properties of some ruthenium and osmium octaethylporphyrins. J. Am. Chem. Soc. 1978, 100 (10), 3015-3024.
13. (a) Che, C. M.; Chung, W. C.; Lai, T. F., Synthesis, reactivity, and X-ray structural characterization of trans-dioxoosmium (VI) porphyrin complexes. Inorg. Chem. 1988, 27 (16), 2801-2804; (b) Djukic, J.-P.; Smith, D. A.; Young, V. G., Jr.; Woo, L. K., Properties and Molecular Structures of Osmium(II) Porphyrin Carbene Complexes: (5,10,15,20-tetra-p-tolylporphyrinato)osmium Di-p-tolylmethylidene and (5,10,15,20-tetra-p-tolylporphyrinato)osmium (Trimethylsilyl)methylidene. Organometallics 1994, 13 (8), 3020-3026; (c) Sawano, K.; Yuge, H.; Miyamoto, T. K., Synthesis of a new oxo-bridged osmium porphyrin carbene complex and its structural characterization. Inorg. Chim. Acta 2005, 358 (6), 1830-1834.
14. (a) Gouterman, M.; Wagniere, G. H.; Snyder, L. C., Spectra of Porphyrins. Part II. Four Orbital Model. J. Mol. Spectr. 1963, 11, 108-127; (b) Gouterman, M., Spectra of Porphyrins. J. Mol. Spectr. 1961, 6, 138-163.

指導教授

蔡惠旭

審核日期

2020-7-28

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