A series of seven-coordinated monoporphyrinate rare-earth(III) complexes featuring a novel tripodal tin-chelated trisphosphineoxide scorpionate ligand with the general formula [(TPP)Ln(PPh₂O)₃Sn] (Ln = Y, La, Dy, Er, Ho, Yb; TPP = 5,10,15,20-tetraphenylporphyrinate) were synthesized by reactions of the potassium tripodal scorpionate ligand [Sn(PPh₂O)₃K] with porphyrinate rare-earth metal chlorides [(TPP)LnCl(dme)] (Ln = Y, Dy, Er, Ho, Yb) or porphyrinate lanthanum borohydride [(TPP)LaBH₄(thf)₂]. The complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy, and ion mobility mass spectrometry. All complexes emit weak red TPP-based fluorescence, accompanied by near-infrared emission of Er, Ho (rather weak), and Yb (relatively intense with a quantum yield of 1% in dichloromethane solution) of the corresponding complexes. Despite the low intensity, the red fluorescence is characteristic (as referred to the parent free-base TPP) and can be used together with optical absorption for analytical evaluation. Similar photophysical properties can be expected for monoporphyrinate rare-earth metal complexes of other tripodal ligands with a similar binding to the (TPP)Ln moiety.

中文翻译：

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锡螯合的三磷酸氢氧化氢蝎酸盐稀土卟啉酸盐复合物：合成和光物理性质


一系列七配位的单卟啉酸稀土 （III） 配合物，具有新型三足锡螯合三磷酸氧化氢蝎酸盐配体，通式为 [（TPP）Ln（PPh₂O）₃Sn] （Ln = Y， La， Dy， Er， Ho， Yb;TPP = 5,10,15,20-四苯基卟啉酸酯）是通过三足蝎酸钾配体 [Sn（PPh₂O）₃K] 与卟啉酸稀土金属氯化物 [（TPP）LnCl（dme）] （Ln = Y， Dy， Er， Ho， Yb） 或卟啉硼氢化镧 [（TPP）LaBH₄（thf）₂] 反应合成的。通过单晶 X 射线衍射、NMR 光谱和离子迁移质谱对复合物进行了表征。所有配合物都发出基于TPP的微弱红色荧光，并伴有相应配合物的Er、Ho（相当弱）和Yb（相对较强，在二氯甲烷溶液中量子产率为1%）的近红外发射。尽管强度低，但红色荧光具有特征性（称为母体游离碱 TPP），可与光吸收一起用于分析评估。对于其他三足配体的单卟啉稀土金属配合物，可以预期类似的光物理特性，这些配合物与 （TPP）Ln 部分具有相似的结合。