Institute of Analytical Chemistry and Food Chemistry, Graz University of Technology, Stremayrgasse 18, A-8010 Graz, Austria.
Inorg Chem. 2010 Oct 18;49(20):9333-42. doi: 10.1021/ic100955z.
A series of π-extended phosphorescent palladium(II) and platinum(II) porphyrin complexes were synthesized, in which additional benzene rings are fused radially onto at least one of the four peripheral benzo groups. The photophysical properties of the metalloporphyrins palladium(II)-meso-tetra-(4-fluorophenyl)mononaphthotribenzoporphyrin (Pd1NF), cis-palladium(II)-meso-tetra-(4-fluorophenyl)dibenzodinaphthoporphyrin (Pd2NF), and palladium(II)-meso-tetra-(4-fluorophenyl)monobenzotrinaphthoporphyrin (Pd3NF) and the corresponding platinum(II) compounds (Pt1NF, cis-Pt2NF, Pt3NF) were investigated. The compounds under investigation absorb intensively in the near-infrared region (628-691 nm) and emit at room temperature at 815-882 nm. Phosphorescence quantum yields of the platinum(II) porphyrins range from 25 to 53% with luminescence decay times of 21 to 44 μs in deoxygenated toluene solutions at room temperature. The corresponding palladium(II) complexes exhibit quantum yields in the range of 7 to 18% with lifetimes of 106 to 206 μs. Density functional theory (DFT) calculations revealed nonplanar geometries for all complexes and corroborate the absorption characteristics. The subsequent π extension of the porphyrin system leads to near-infrared absorbing oxygen indicators with tailor-made luminescence properties as well as tunable oxygen sensitivity.
一系列π-扩展的磷光钯(II)和铂(II)卟啉配合物被合成，其中额外的苯环以放射状方式融合到至少一个四个外围苯环上。金属卟啉的光物理性质研究了钯(II)-meso-四-(4-氟苯基)单萘三苯并卟啉(Pd1NF)、顺式-钯(II)-meso-四-(4-氟苯基)二苯并二萘并卟啉(Pd2NF)和钯(II)-meso-四-(4-氟苯基)单苯并三萘并卟啉(Pd3NF)以及相应的铂(II)化合物(Pt1NF、顺式-Pt2NF、Pt3NF)。所研究的化合物在近红外区域(628-691nm)强烈吸收，并在室温下在 815-882nm 处发射。铂(II)卟啉的磷光量子产率在 25%至 53%之间，在室温下脱氧甲苯溶液中的荧光衰减时间为 21 至 44μs。相应的钯(II)配合物的量子产率在 7%至 18%之间，寿命为 106 至 206μs。密度泛函理论(DFT)计算表明所有配合物均具有非平面几何形状，并证实了吸收特性。卟啉体系的随后π扩展导致具有定制发光性能和可调氧敏性的近红外吸收氧指示剂。
