Isolation and Spectroscopic Characterization of Protonated Mixed [Tetrakis (4-pyridyl)porphyrinato]

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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+. 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 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) (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+.
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