作为Be^(2+)磷光探针的含9-冠-3的铱配合物

Beryllium Ion-Selective Phosphorescence Probes Based on 9-Crown-3 Ether Iridium Complexes

以4′-(2-苯并噻唑基)苯并-9-冠-3(BTZ9C3)为主配体,用2,2′-联吡啶(bpy)及3-三氟甲基-5-(2′-吡啶基)-1,2-二唑(Hfppz)辅助配体分别合成了离子型铱配合物[Ir(BTZ9C3)2(bpy)]PF6(1)和中性铱配合物[Ir(BTZ9C3)2(fppz)](2)。配合物的结构通过核磁、高分辨质谱进行了表征,并测定了配合物1的单晶结构。对它们光物理性能的研究表明,2种配合物掺杂在PMMA中的发光为黄绿光发射,配合物1的发光波长为535 nm,配合物2的发光波长为541 nm,发光量子效率分别为10.8%,45.0%,发光寿命分别为3.01和2.58μs,为典型的磷光发射。通过循环伏安法测得配合物1和2的HOMO能级分别为-5.60和-5.35 eV。2种配合物对Be2+都有发光增强的选择性识别效果,化学计量比为1∶2,最低检测限低至6.0μmol·L-1。抗干扰能力方面,离子型配合物1的抗干扰能力较好,而中性配合物2受Al3+的干扰较大。

Ionic iridium complex [Ir(BTZ9C3)2(bpy)]PF6 (1) and neutral iridium complex [Ir(BTZ9C3)2(fppz)](2) were synthesized with 4′-(2-benzothiazolyl)benzo-9-crown-3 ether (BTZ9C3) primary ligand and different ancillary ligands: 2,2′-bipyridine (bpy) and 3-trifluoromethyl-5-(2′-pyridyl)-1,2-diazole (Hfppz). The structures of the complexes were characterized by NMR, high resolution mass spectrometry, and the single crystal structure of 1 was determined by X-ray structural analysis. All these complexes showed a strong Kelly phosphorescent emission. The photoluminescence spectra of complexes 1 and 2 in PMMA (1%(w/w)) showed emission maximum at 535 and 541 nm, respectively. Their quantum efficiencies were 10.8% and 45.0% and the luminescence lifetimes were 3.01 and 2.58 μs. By means of the cyclic voltammogram, the HOMO levels of complexes 1 and 2 were calculated to be -5.60 and -5.35 eV. Both complexes displayed a high selectivity for Be2+ among relevant metal ions, and exhibited luminescence enhancement effect in the presence of Be2+. The stoichiometric ratio of iridium complexes responding to Be2+ was determined to be 1∶2, and the detection limit is down to 6.0 μmol·L^-1. The ionic iridium complex 1 has good anti-disturbance, however the neutral iridium complex 2 is greatly interfered by Al3+. CCDC: 1844315, 1.