The treatment of tetrakis (4-pyridyl) porphyrin H2TPyP with a hydrated rare earth (III) acetylacetonate RE(acac)3 · nH2O (RE=Y, Eu, Gd) in 1,2, 4-trichlorobenzene (TCB) pro- duced a monomeric porphyrinato rare e...The treatment of tetrakis (4-pyridyl) porphyrin H2TPyP with a hydrated rare earth (III) acetylacetonate RE(acac)3 · nH2O (RE=Y, Eu, Gd) in 1,2, 4-trichlorobenzene (TCB) pro- duced a monomeric porphyrinato rare earth compound RE (TPyP) acac, which further reacted with dicyanobenzene in amyl alcohol in the presence of 1, 8-diazabicyclo [5. 4. 0] undec-7-ene (DBU), giving HRE(TPyP) (Pc) in a good yield. Upon exposure to air, part of the protonated mixed double-deckers in CHC13 solutions converted slowly to the corresponding neutral complexes RE (TPyP) (Pc). These protonated complexes were characterized by means of UV-V is, IR, NMR, mass spectroscopies. The quaternarization of these protonated mixed double-deckers with methyl iodide produced the salts of tetramethylated cations [HRE(TMPyP) (Pc)]4+.展开更多
The water soluble tetra p sulfonatophenylporphyrinatolanthanide, [Ln·TPPS·OH ·2imidazole] ·3H 2O(Ln=Tb～Yb), were synthesized and characterized. Their stability and complex constants were...The water soluble tetra p sulfonatophenylporphyrinatolanthanide, [Ln·TPPS·OH ·2imidazole] ·3H 2O(Ln=Tb～Yb), were synthesized and characterized. Their stability and complex constants were also studied and determined. The structural formula of the lanthanide porphyrins was proposed too. The lanthanide atom is sitting above the porphyrin plane. For the lanthanide porphyrin complexes, the complex becomes more stable and the reduction potential has a slight shift to more positive values as the atomic number increases from Tb to Yb. The mechanism of electrode processes for these lanthanidee porphyrin complexes were investigated in details.展开更多
The coordination number of the gadolinium atom and bond distances in the crystal of inonomeric porphyrinate,[Gd(TPP)acac-8H2O 3TCB] (TCB: 1,2,4-trichlorobenzene,acac: anion of acetylacetone),were determined by EXAFS m...The coordination number of the gadolinium atom and bond distances in the crystal of inonomeric porphyrinate,[Gd(TPP)acac-8H2O 3TCB] (TCB: 1,2,4-trichlorobenzene,acac: anion of acetylacetone),were determined by EXAFS method.The Gd atom is eight-coordinated to the four nitrogen atoms of a tetraphenylporphyrin ring,to the two oxygen atoms of one acetylacetonato anion and to two water molecules with Gd-N=0.232 nm,Gd-O=0.243 nm.展开更多
基金Educational Ministry of China, Natural Science Foundation of China (Grant No. 29701002, 29992590-4), the Visiting Scholar Foun
文摘The treatment of tetrakis (4-pyridyl) porphyrin H2TPyP with a hydrated rare earth (III) acetylacetonate RE(acac)3 · nH2O (RE=Y, Eu, Gd) in 1,2, 4-trichlorobenzene (TCB) pro- duced a monomeric porphyrinato rare earth compound RE (TPyP) acac, which further reacted with dicyanobenzene in amyl alcohol in the presence of 1, 8-diazabicyclo [5. 4. 0] undec-7-ene (DBU), giving HRE(TPyP) (Pc) in a good yield. Upon exposure to air, part of the protonated mixed double-deckers in CHC13 solutions converted slowly to the corresponding neutral complexes RE (TPyP) (Pc). These protonated complexes were characterized by means of UV-V is, IR, NMR, mass spectroscopies. The quaternarization of these protonated mixed double-deckers with methyl iodide produced the salts of tetramethylated cations [HRE(TMPyP) (Pc)]4+.
文摘The water soluble tetra p sulfonatophenylporphyrinatolanthanide, [Ln·TPPS·OH ·2imidazole] ·3H 2O(Ln=Tb～Yb), were synthesized and characterized. Their stability and complex constants were also studied and determined. The structural formula of the lanthanide porphyrins was proposed too. The lanthanide atom is sitting above the porphyrin plane. For the lanthanide porphyrin complexes, the complex becomes more stable and the reduction potential has a slight shift to more positive values as the atomic number increases from Tb to Yb. The mechanism of electrode processes for these lanthanidee porphyrin complexes were investigated in details.
基金Project supported by the National Natural Science Foundation of China (No. 29701002)the Sate Educational Committee of ChinaShandong University of China
文摘The coordination number of the gadolinium atom and bond distances in the crystal of inonomeric porphyrinate,[Gd(TPP)acac-8H2O 3TCB] (TCB: 1,2,4-trichlorobenzene,acac: anion of acetylacetone),were determined by EXAFS method.The Gd atom is eight-coordinated to the four nitrogen atoms of a tetraphenylporphyrin ring,to the two oxygen atoms of one acetylacetonato anion and to two water molecules with Gd-N=0.232 nm,Gd-O=0.243 nm.
