双环金属化铱（III）配合物作为高效的单线态氧敏化剂。
Bis-cyclometalated Ir(III) complexes as efficient singlet oxygen sensitizers.
作者信息
Gao Ruomei, Ho David G, Hernandez Billy, Selke Matthias, Murphy Drew, Djurovich Peter I, Thompson Mark E
机构信息
Department of Chemistry, California State University at Los Angeles, Los Angeles, CA 90032, USA.
出版信息
J Am Chem Soc. 2002 Dec 18;124(50):14828-9. doi: 10.1021/ja0280729.
We report the singlet oxygen sensitization properties of a series of bis-cyclometalated Ir(III) complexes (i.e., (bt)2Ir(acac), (bsn)2Ir(acac), and (pq)2Ir(acac); bt = 2-phenylbenzothiazole, bsn = 2-(1-naphthyl)benzothiazole, pq = 2-phenylquinoline, and acac = acetylacetonate). Complexes with acetylacetonate ancillary ligands give singlet oxygen quantum yields near unity (PhiDelta = (0.7-1.0) +/- 0.1), whether exciting the ligand-based state or the lowest energy excited state (MLCT + 3LC). The singlet oxygen quenching rates for these beta-diketonate complexes were found to be small [(5 +/- 2) x 105 to (6 +/- 0.2) x 106 M-1 s-1], roughly 3 orders of magnitude slower than the corresponding phosphorescence quenching rate. Similar complexes were prepared with glycine or pyridine tethered to the Ir(III) center (i.e., (bsn)2Ir(gly) and (bt)2Ir(py)Cl; gly = glycine and py = pyridine). The glycine and pyridine derivatives give high singlet oxygen yields (PhiDelta = (0.7-1.0) +/- 0.1).
我们报道了一系列双环金属化铱（III）配合物（即(bt)2Ir(acac)、(bsn)2Ir(acac)和(pq)2Ir(acac)；bt = 2-苯基苯并噻唑，bsn = 2-(1-萘基)苯并噻唑，pq = 2-苯基喹啉，acac = 乙酰丙酮）的单线态氧敏化性质。无论激发基于配体的态还是最低能量激发态（MLCT + 3LC），具有乙酰丙酮辅助配体的配合物都能给出接近1的单线态氧量子产率（PhiDelta = (0.7 - 1.0) ± 0.1）。发现这些β-二酮配合物的单线态氧猝灭速率较小[ (5 ± 2) × 105至(6 ± 0.2) × 106 M-1 s-1 ]，比相应的磷光猝灭速率慢约3个数量级。制备了类似的配合物，其中甘氨酸或吡啶连接到铱（III）中心（即(bsn)2Ir(gly)和(bt)2Ir(py)Cl；gly = 甘氨酸，py = 吡啶）。甘氨酸和吡啶衍生物给出高单线态氧产率（PhiDelta = (0.7 - 1.0) ± 0.1）。
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