Synthesis and spectroscopic characterization of Ni, Zn, Pd and Pt tetra(pentafluorophenyl)porpholactone with comparisons to Mg, Zn, Y, Pd and Pt metal complexes of tetra(pentafluorophenyl)porphine

Abstract

Ni , Zn , Pd and Pt tetra(pentafluorophenyl)porpholactone (TFPL) were synthesized and identified by their optical and mass spectra. The lactone ring was produced from the parent free-base porphyrin using silver nitrate and oxalic acid with a yield of 73%, and the metals were inserted by standard procedures from metal salts. The compounds show intense Soret Bands in the region 390-420 nm. The longest wavelength visible absorbance peaks, in the region 572-608 nm, are weaker than the Soret peaks by a factor of only ~3 for the Ni , Pd , and Pt complexes but a factor of ~10 for the free-base and Zn complexes. As found with other metalloporphyrins the Ni complex is dark, Zn shows fluorescence and Pd and Pt complexes show strong phosphorescence. The Pd complex also shows a weak fluorescence not quenched by oxygen. The phosphorescence lifetimes of Pd and Pt complexes of TFPL in 3-methylpentane at 77 K are, respectively, ~1 ms and ~70 μs, about 60% that of the TFPP complexes. The wavelengths of phosphorescence emission, 733 nm and 758 nm for PtTFPL and PdTFPL, respectively, are sufficiently red-shifted so that these pressure sensitive luminophors can be included in the same pressure sensitive paint (PSP) as Eu complexes, whose emission at ~615 nm can serve as a temperature sensor. The fluorescences of Mg , Zn , and Y(TFPP) show weak origin bands, making them suitable as unquenched references for PSP.

Exceptional Oxygen Sensing Properties of New Blue Light‐Excitable Highly Luminescent Europium(III) and Gadolinium(III) Complexes

“…[1][2][3][4] Most oxygen sensors employ such widespread indicators as ruthenium(II) polypyridyl complexes, [5][6][7] platinum(II) and palladium(II) porphyrins [8][9][10][11] and their analogues. [12][13][14] Other luminescent indicators are less popular which is explained by their inferior photophysical properties (low absorption coefficients and luminescence quantum yields, short luminescence decay times, poor photostability etc.) [3]or by complicated multistep synthesis.…”

Observation of phenyl-fused porphyrinoids during the ESI mass spectrometric analysis of meso-pentafluorophenyl-substituted porphyrin and corrole

“…The quenching of the photo-excited triplet state of Pt(II) complexes of porphyrins is the origin of their utility in pressure-sensitive paints (PSP) that allow for the continuous mapping of surface pressures [12][13][14][15][16]. We have found that the use of the fluorinated ligand T F PP in PSP formulations increases the phosphorescence lifetime of the paints and leads to photo-stable coatings, presumably because of the protection the pentafluorophenyl groups provide from singletoxygen-mediated oxidative degradation of the chromophore [13][14][15][16]. Further, T F PP was suggested as a chemically inert and strongly light-absorbing matrix in MALDI-TOF mass spectrometry [17].…”

A convenient and eco-friendly way to synthesize Pt(II) and Pd(II) porphyrins in ionic liquids by microwave activation

“…These side reactions may also give other by-products during metalation of porphyrins in DMF. It is also noted that electron-withdrawing groups attached to the porphyrin periphery also promote the formation of other (Lai et al 2004;Khalil et al 2002). Recently, it was argued that microwave-assisted methods might be less beneficial for the metalloporphyrin synthesis because of some limitations of the traditional solvents (Dean et al 2008).…”