高剛性咔唑鉗形配位基對 Cu₂N₂ 核心結構及螢光性質的影響;Effect of High Rigidity Carbazole Pincer Ligand to {Cu2N2} Core Structures with Fluorescent Properties

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题名:	高剛性咔唑鉗形配位基對 Cu₂N₂ 核心結構及螢光性質的影響;Effect of High Rigidity Carbazole Pincer Ligand to {Cu2N2} Core Structures with Fluorescent Properties
作者:	趙薪;HSIN, CHAO
贡献者:	化學學系
关键词:	銅錯合物;螢光;磷光;電子傳遞酶
日期:	2025-07-29
上传时间:	2025-10-17 11:25:49 (UTC+8)
出版者:	國立中央大學
摘要:	本研究合成了一系列由HCzR′(PyrR)2配位的的Cu1+錯合物-[CzR′(PyrR)2Cu]2 (R = Me, iPr, Ph, R′ = H, tBu)，此系列錯合物為少見的全氮配位雙核錯合物，其中心由{Cu2N2}菱形核心組成。其中大部份錯合物在循環伏安法下測得兩個可逆的氧化還原對，且部分錯合物能氧化並單離出Cu1+Cu1+、Cu1+Cu2+、Cu2+Cu2+等三個氧化態。而單晶結構顯示此系列錯合物的Cu1+…Cu1+距離約2.6 Å至2.7 Å，且現隨著氧化數增而改變。在mixed-valent的氧化態下，此研究以EPR鑑定其屬於Robin-Day Class II的非定域性。並以NMR line-broadening 技術估算Cu1+Cu1+與氧化後的電子自交換速率可達約104到106 M-1s-1。此系列Cu1+錯合物具有螢光性質，因此本論文也討論了不同取代基對螢光性質的影響，並發現此系列Cu1+錯合物的量子產率及螢光壽命皆有不錯的表現。;In this study, a series of Cu(I) complexes coordinated by HCzR′(PyrR)₂ ligands, with the general formula [CzR′(PyrR)₂Cu]₂ (R = Me, iPr, Ph; R′ = H, tBu), were synthesized. These complexes represent a rare class of dinuclear, all-nitrogen-ligated Cu1+ compounds, featuring a {Cu₂N₂} diamond core at their center. Most of the complexes exhibit two reversible redox couples in cyclic voltammetry, and several can be oxidized and isolated in three distinct oxidation states: Cu1+Cu1+, Cu1+Cu2+, and Cu2+Cu2+. SXRD reveals that the Cu···Cu distances in the Cu1+Cu1+ state range from approximately 2.6 Å to 2.7 Å, with variations observed upon oxidation. In the mixed-valent states, EPR spectroscopy indicates Robin-Day Class II behavior, suggesting a partially delocalized electronic structure. Additionally, electron self-exchange rates between the Cu(I)Cu(I) and oxidized species were estimated by NMR line-broadening experiments, yielding values on the order of 104 to 106 M-1s-1. These Cu1+ complexes also exhibit photoluminescence. The photophysical properties, including quantum yields and emission lifetimes, were measured, and the influence of different substituents on their luminescent behavior was discussed. Overall, the complexes demonstrate promising luminescent performance.
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