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| 两种离子型铱配合物的合成、光物理性质及对OH-的检测 |
| Synthesis, photophysical properties and OH- recognition of two cationic iridium complexes |
| 投稿时间：2022-12-12 |
| DOI： |
| 中文关键词: 铱配合物 合成 表征 发光性质 检测OH- 磷光增强 |
| 英文关键词: iridium complex synthesis characterization luminescent property OH- sensing phosphorescence enhancement |
| 基金项目:河北省自然科学基金(B2022202060)；国家自然科学基金(21501042) |
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| 中文摘要: |
| 以两种2,2’-联吡啶衍生物为中性配体，2-(3-氟苯基)吡啶为环金属配体，合成了两种新型的离子型Ir(Ⅲ)配合物Ir1和Ir2。利用核磁、质谱和晶体结构分析确认了配合物Ir1和Ir2的结构。配合物Ir1和Ir2在CH2Cl2溶液中的最大发射波长分别为570和528 nm，为橙红光和黄光。两种配合物在无氧CH2Cl2溶液中的量子产率分别为0.88和0.57，磷光寿命分别为2.43和2.40 μs。通过理论计算详细讨论了中性配体的取代基种类对其光谱性质的影响。在配合物Ir1的DMSO/H2O溶液中加入OH-后，其发射峰强度提高了近100倍，溶液的发光颜色由红色变为明亮的绿色，检出限为8.47×10-6 mol/L。机理研究表明，OH-取代了Ir1的中性配体上的溴取代基，形成了新的含有羟基的配合物，从而改变了Ir1的光谱特性，实现对OH-的高选择性和高灵敏度检测。 |
| 英文摘要: |
| Two novel cationic iridium(Ⅲ) complexes, Ir1 and Ir2, were synthesized by using 2,2’-bi- pyridine derivatives as neutral ligands and 2-(3-fluorophenyl)pyridine as cyclometalated ligands. Their molecular structures were characterized via 1H NMR, MS and X-ray analysis. The maximum emission peak of complexes Ir1 and Ir2 was located at 570 and 528 nm, respectively, in CH2Cl2 solution, showing orange-red and yellow luminescence. The quantum yield of Ir1 and Ir2 was measured to be 0.88 and 0.57, respectively, with a lifespan of 2.40~2.43 μs in oxygen-free solution. The effect of substituents on the spectral properties of the complexes was discussed in detail by theoretical calculation. When OH- was added into the DMSO/H2O solution of Ir1, it showed a 100-fold enhanced emission and the luminescence color of the solution shifted from red to bright green, and the detection limit for OH-was 8.47×10-6 mol/L. The sensing mechanism of Ir1 may be that OH- substitue the bromide groups on the neutral ligand of complex Ir1, forming a new species containing hydroxyl groups. The substitution will change the spectral properties of the complex and achieve both high selectivity and sensitivity for the detection of OH-. |
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