| 摘要: | 染料敏化太陽能電池 Dye-sensitized solar cells (簡稱DSCs)至今已發展數十年，其中釕錯合物染料為具代表性的系列，於本研究中使用碳、矽、氮、磷、氧、硫等不同原子與釕金屬鍵結，最終成功合成出以氮碳為配位原子與釕鍵結的雜環錯合物染料HBC23；以及具光致變色(經照光後可從氮硫變為氮氧做配位原子的釕錯合物)的染料PC1；其中選了三個含矽的配位基8,8’-(methylsilanediyl)diquinoline (NSiN)、8-dimethylsilylquinoline (NSi) 及(2-(dimethylsilyl)phenyl)diphenylphosphane (PSi)與釕金屬錯合，但僅NSiN成功與釕鍵結形成含乙酯基的錯合物，然而在隨後的水解反應中被分解；根據計算上述的不同原子與釕鍵結產生的錯合物鍵能則可發現：釕矽鍵能最低(-309 kJ/mol)，而HBC23以有sp2電子的碳與釕鍵結之鍵能最高(-1070 kJ/mol)，在此假設了一錯合物Ru-NC用於計算鍵能(以8-Isopropylquinoline與釕錯合，結構與NSi相似僅將矽改為碳)，其sp3電子的碳與釕的鍵能僅-463 kJ/mol，因此是需具有sp2電子的碳才能與釕形成強鍵結；具光致變色性質的染料PC1鍵能經計算是釕氧鍵(-757 kJ/mol)大於釕硫鍵(-697 kJ/mol)，因此可解釋染料在照光激發後會傾向形成更穩定的釕氧鍵錯合物，並在照光10分鐘後於波長510 nm處吸收係數提升了4300 M-1 cm-1。;Dye-sensitized solar cells (DSCs) have been under development for several decades, with ruthenium metal complex dyes being a representative series. In this study, various atoms such as carbon, silicon, nitrogen, phosphorus, oxygen, and sulfur were used to bond with ruthenium metal. Finally, we successfully synthesized of the heterocyclic complex dye HBC23, which uses nitrogen and carbon as coordinating atoms bonded to ruthenium. Additionally, we synthesized the dye PC1, which exhibits photochromic properties (it can change from nitrogen-sulfur to nitrogen-oxygen coordination upon illumination). Three silicon-containing chelating agents were selected: 8,8′-(methylsilanediyl)diquinoline (NSiN), 8-dimethylsilylquinoline (NSi), and (2-(dimethylsilyl)phenyl) diphenylphosphane (PSi) to form complexes with ruthenium metal. Among these, only NSiN successfully bonded with ruthenium to form an ethyl ester complex, which subsequently decomposed during a hydrolysis reaction. Calculated bond energies for these various atom-ruthenium complexes revealed that the ruthenium-silicon bond has the lowest bond energy (-309 kJ/mol), while the HBC23 complex, featuring sp2 carbon bonded to ruthenium, has the highest bond energy (-1070 kJ/mol). To further explore this, we hypothesized a complex Ru-NC for bond energy calculation (formed by bonding 8-isopropylquinoline with ruthenium, similar in structure to NSi but with silicon replaced by carbon). The bond energy of sp3 carbon bonded to ruthenium is only -463 kJ/mol, indicating that only sp2 carbon can form a strong bond with ruthenium. For the photochromic dye PC1, the calculated bond energies show that the ruthenium-oxygen bond (-757 kJ/mol) is stronger than the ruthenium-sulfur bond (-697 kJ/mol). This explains why the dye tends to form a more stable ruthenium-oxygen complex upon absorbing energy. After 10 minutes of illumination, the absorption coefficient at a wavelength of 510 nm increased by 4300 M-1 cm-1. |
