| DC 欄位 |
值 |
語言 |
| DC.contributor | 化學學系 | zh_TW |
| DC.creator | 林慧絜 | zh_TW |
| DC.creator | Hui-Jie Lin | en_US |
| dc.date.accessioned | 2020-7-28T07:39:07Z | |
| dc.date.available | 2020-7-28T07:39:07Z | |
| dc.date.issued | 2020 | |
| dc.identifier.uri | http://ir.lib.ncu.edu.tw:444/thesis/view_etd.asp?URN=107223064 | |
| dc.contributor.department | 化學學系 | zh_TW |
| DC.description | 國立中央大學 | zh_TW |
| DC.description | National Central University | en_US |
| dc.description.abstract | 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。 | zh_TW |
| dc.description.abstract | 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. | en_US |
| DC.subject | DSSC | zh_TW |
| DC.subject | porphyrin | zh_TW |
| DC.subject | Spin-Orbit Coupling | zh_TW |
| DC.subject | Metalloporphyrin | zh_TW |
| DC.title | 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 | en_US |
| dc.language.iso | en_US | en_US |
| DC.type | 博碩士論文 | zh_TW |
| DC.type | thesis | en_US |
| DC.publisher | National Central University | en_US |