佟鑫, 葛泽荣, 赵世盛, 李文豪, 楚曦, 李红岩. 高效红光铱配合物的合成、光物理性质和理论计算[J]. 云南大学学报(自然科学版), 2022, 44(5): 1012-1017. doi: 10.7540/j.ynu.20210581
引用本文: 佟鑫, 葛泽荣, 赵世盛, 李文豪, 楚曦, 李红岩. 高效红光铱配合物的合成、光物理性质和理论计算[J]. 云南大学学报(自然科学版), 2022, 44(5): 1012-1017. doi: 10.7540/j.ynu.20210581
TONG Xin, GE Ze-rong, ZHAO Shi-sheng, LI Wen-hao, CHU Xi, LI Hong-yan. On synthesis, photophysical properties and theoretical study of a high efficiency red iridium complex[J]. Journal of Yunnan University: Natural Sciences Edition, 2022, 44(5): 1012-1017. DOI: 10.7540/j.ynu.20210581
Citation: TONG Xin, GE Ze-rong, ZHAO Shi-sheng, LI Wen-hao, CHU Xi, LI Hong-yan. On synthesis, photophysical properties and theoretical study of a high efficiency red iridium complex[J]. Journal of Yunnan University: Natural Sciences Edition, 2022, 44(5): 1012-1017. DOI: 10.7540/j.ynu.20210581

高效红光铱配合物的合成、光物理性质和理论计算

On synthesis, photophysical properties and theoretical study of a high efficiency red iridium complex

  • 摘要: 以1−(3−氟苯基)异喹啉(3F−piq)为环金属配体,4,4′−二叔丁基−2,2′−联吡啶(dtb-bpy)为中性配体,六氟磷酸根为阴离子成功合成了一种离子型铱配合物(3F−piq)2Ir(dtb-bpy)(PF6) ( Ir1 ). 晶体结构表明中心离子Ir的几何构型为扭曲八面体构型. 在327 nm的激发条件下,配合物 Ir1 在CH2Cl2溶液中的发射峰位于590 nm,为明亮的红光,量子效率为55%. 电化学研究表明,配合物 Ir1 在0.8 ~ 1.5 V (vs. Ag+/Ag)范围内出现一对可逆的氧化还原峰,归属于Ir3+/Ir4+的氧化还原过程. 理论计算表明最高占据分子轨道(HOMO)主要分布在金属铱的d轨道和环金属配体上,而最低空分子轨道(LUMO)主要分布于中性配体上.

     

    Abstract: A cationic iridium cyclometalated complex (3F−piq)2Ir(dtb-bpy)(PF6)( Ir1 ) with 1-(3-fluorophenyl) isoquinoline (3F−piq) as a cyclometalated ligand, 4,4′-di-tert-butyl-2,2′-bipyridine (dtb-bpy) as a neutral ligand and hexafluorophosphate as an anion has been synthesized successfully. X-ray crystallographic analysis reveals that the iridium center adopts a distorted octahedral coordination geometry. Upon excitation at 327 nm, the complex Ir1 exhibit strong red phosphorescence (λem=590 nm) with quantum efficiencies of 55% in oxygen-free dichloromethane solution at room temperature. Electrochemical study shows a quasireversible oxidation with potentials at 0.80−1.50 V (vs. Ag+/Ag), which is attributed to the redox process of Ir3+/Ir4+. Theoretical calculation shows that the highest occupied molecular orbital (HOMO) mostly distribute over the d orbitals of the iridium atom and the cyclometalated ligand, while the lowest unoccupied molecular orbital (LUMO) is mainly localized on the neutral ligand.

     

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