作为Be~(2+)磷光探针的含9-冠-3的铱配合物
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摘要
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 1was 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 and541 nm, respectively. Their quantum efficiencies were 10.8% and 45.0% and the luminescence lifetimes were3.01 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 e V. 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+.
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 1was 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 and541 nm, respectively. Their quantum efficiencies were 10.8% and 45.0% and the luminescence lifetimes were3.01 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 e V. 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+.
引文
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[3] Shi W Y, Bai L Q, Guo J, et al. Sens. Actuators B, 2016,223:671-678
[4] Isildak I, Attar A, Demir E, et al. Curr. Anal. Chem., 2018,14:43-48
[5] Li J, Ma F, Wei X, et al. Anal. Chim. Acta, 2015,871:51-56
[6] Wang J, Thongngamdee S, Lu D. Anal. Chim. Acta, 2006,564:248-252
[7] Ganjali M R, Ghorbani M, Norouzi P, et al. Sens. Actuators B, 2004,100:315-319
[8] Ganjali M R, Rahimi-Nasrabadi M, Maddah B, et al. Talanta,2004,63:899-906
[9] Soleymanpour A, Rad N A, Niknam K. Sens. Actuators B,2006,114:740-746
[10]Gupta V K, Singh A K, Mergu N. Anal. Chim. Acta, 2012,749:44-50
[11]Ji X, Shi W, Zhang S, et al. Anal. Chim. Acta, 2012,728:77-85
[12]Shi W Y, Bai L Q, Guo J, et al. Sens. Actuators B, 2016,223:671-678
[13]Guerchais V, Fillaut J L. Coord. Chem. Rev., 2011,255:2448-2457
[14]Buchanan G W, Driega A B, Moghimi A, et al. Can. J. Chem.,1993,71:951-959
[15]Dondoni A, Mara A, Scherrmann M C, et al. Chem. Eur. J.,2001,7(7):1371-1382
[16]PAN Miao(潘淼), LI Si-Hua(李思华), CHENG Mao-Ling(程茂玲), et al. Chinese J. Inorg. Chem.(无机化学学报), 2018,34(4):627-632
[17]Tong B H, Qiang J Y, Mei Q B, et al. Z. Naturforsch. B:Chem. Sci., 2012,67b:213-218
[18]TONG Bi-Hai(童碧海), MEI Qun-Bo(梅群波), LI Zhi-Wen(李志文), et al. Acta Chim. Sinica(化学学报), 2012,70(23):2451-2456
[19]Ma D X, Qiu Y, Duan L. Adv. Funct. Mater., 2016,26:3438-3445
[20]Zhao Q, Li F Y, Huang C H. Chem. Soc. Rev., 2010,39:3007-3030
[21]Wang Y C, Xie Y Y, Qu H E, et al. J. Org. Chem., 2014,79:4463-4469
[22]Sheldrick G M. SHELX-97, Program for the Solution and the Refinement of Crystal Structures, University of G觟ttingen,Germany, 1997.