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PubMed · 14805992

[Luminescence microscopy].

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OTTO. 1950. [Luminescence microscopy].. https://pubmed.ncbi.nlm.nih.gov/14805992/

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Synthesis and photophysical properties of meso-substituted bisporphyrins: comparative study of phosphorescence quenching for dioxygen sensing.

The 4,6-bis(10-mesityl-5,15-di-p-tolylporpyrinyl)dibenzothiophene (H4DPSN) free base was obtained in five steps from commercially available materials. The metalation of DPSN2- with zinc(II), copper(II), and palladium(II) led to three new homobimetallic systems, (Zn)2DPSN, (Cu)2DPSN, and (Pd)2DPSN, respectively. The cofacial structures of these molecules offer the possibility of having dioxygen molecules inside the cavity for a period of time, allowing dynamic (collisional) phosphorescence quenching to be more efficient. The bimolecular excited-state deactivation rate constant for deactivation by dioxygen (kQ: (Pd)2DPB, 2.98x10(9); (Pd)2DPSN, 3.99x10(9); (Pd)2DPX, 6.94x10(9); (Pd)TPP, 8.95x10(9); (Pd)2DPS, 8.95x10(9) M-1 s-1) of (Pd)2DPSN, which exhibits an intense phosphorescence at 699 nm, was compared to those observed for (Pd)TPP, (Pd)2DPS, (Pd)2DPX, and (Pd)2DPB (TPP2-=tetraphenylporphyrin dianion, DPS4-=4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene tetraanion, DPX4-=4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene tetraanion, and DPB4-=1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene tetraanion). These collision-induced deactivation data were interpreted by estimating a series of physical parameters such as the surface area and bisporphyrin radii, the diffusion coefficient of the bismacrocycles, and the theoretical deactivation efficiency for the five compounds addressing the role of steric hindrance of the macrocycles on each other and the aryl groups at the meso positions. For sensing purposes, (Pd)2DPX is characterized by a Stern-Volmer constant kSV of 2.91x10(6) M-1, placing the lower detection limit for [O2] in solution at 0.58 ppm, which is better than that for (Pd)TPP (kSV=2.31x10(6) M-1; lower detection limit of 0.73 ppm), the classically used monoporphyrin complex.

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Synthesis and luminescence of soluble meso-unsubstituted tetrabenzo- and tetranaphtho[2,3]porphyrins.

[Structure: see text]. Syntheses of soluble tetrabenzoporphyrins (TBP) and tetranaphtho[2,3]porphyrins (TNP), with multiple substituents in the conjugated aromatic rings but bearing no substituents in the meso-positions, is reported. Both types of porphyrins were obtained by direct aromatization of precursor porphyrins, annealed with either cyclohexene or dihydronaphthalene fragments. TBPs and TNPs possess powerful absorption bands in the near-infrared (lambda = 610-710 nm, epsilon = 100,000-300,000 M(-1) cm(-1)) and exhibit strong luminescence. Free bases and Zn complexes fluoresce with quantum yields of up to 50%, whereas Pd and Pt complexes phosphoresce in solutions at ambient temperatures. Remarkably, the phosphorescence quantum yields of Pd and Pt TBPs reach as high as 20-50%, which places them among the brightest near-infrared phosphors known to date.

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It was proposed a method of synthesis several 6-styrylo1-1H-pyrazolo[3,4-b]quinolines as promising material for optoelectronics. Particularly, 6-styryl-1,3-diphenyl-1H-pyrazolo[3,4-b]quinolines were prepared by Wadsworth-Emmons reaction. One of advantageous of these materials is stability of their optical spectra versus the possible cis- and trans-transformation. Theoretical and experimental studies of optical absorption and photoluminescence excitation spectra for styryloquinolines were done. They show that the AM1 semi-empirical method gives better results compared to other approaches. We have found that the solvents do not play a role in the behavior of the spectra. The backside-substituted groups do not influence substantially the observed optical spectra.

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