ChemInform Abstract: PHTHALOCYANINES AND RELATED COMPOUNDS. XXIV. SYNTHESIS AND ELECTRONIC ABSORPTION SPECTRA OF TETRA‐1,2‐ AND TETRA‐2,3‐NAPHTHOPORPHYRINS

Kopranenkov, V. N.; Vorotnikov, A. M.; Dashkevich, S. N.; Luk’yanets, E. A.

doi:10.1002/chin.198543338

Cited by 7 publications

(13 citation statements)

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“…45 To assess the relative contributions of distortion and increased π-conjugation, we compiled the experimental and theoretical results from model compounds not containing meso-phenyl substituents that directly compare the data from our series of chromophores. The model compounds are: unsubstituted Zn porphyrin (ZnP), Pd porphyrin (PdP), Zn tetrabenzoporphyrin (ZnTBP), 46 Pd tetrabenzoporphyrin (PdTBP), 46 Zn tetranaphthoporphyrin (Zn-TNP), 13 and Pd tetranaphthoporphyrin (PdTNP). 18 These compounds are all planar in the ground state, which make them useful for understanding spectral red shifts that are due to purely electronic effects.…”

Section: Discussionmentioning

confidence: 99%

“…The NMR spectrum matches that obtained by Ichimura et al, 3 Cheng et al, 4 and Ito et al 9 ZnTPTNP. This synthesis followed the template method by Kopranenkov et al 13 A mixture of 2,3-naphthalenecarboxyimide, zinc benzoate, and phenylacetic acid (with molar ratio 1:1:2) was used. The reaction product was purified by repeated chromatography with chloroform first and then with chloroform/ hexanes/THF (30:10:1) on a column of neutral aluminum oxide.…”

Section: Methodsmentioning

confidence: 99%

“…The qualitative observations, e.g., red shifts in the ground and excited state spectra with annulation, are discussed, but no attempt to quantify the data was made. [11][12][13][14][15][16] We synthesized the same series of chromophores and report a detailed quantitative study of photophysical parameters. In addition, calculations using timedependent density functional theory (TDDFT) were carried out to interpret the observed spectra and to shed light on the origin of the spectral shifts.…”

Section: Introductionmentioning

confidence: 99%

“…The metalated meso-tetraphenyltetrabenzoporphyrin (MTPT-BP) and meso-tetraphenyl [2,3]tetranaphthoporphyrin (MTPTNP) shown in Figure 1 were previously synthesized, [3][4][5][6][7][8][9][10][11][12][13] but relatively few thorough and comprehensive studies were carried out. Several papers have been published in which MTPTBP and MTPTNP are studied and compared with similar systems that do not contain the meso-phenyl groups, i.e., tetrabenzoporphyrin (MTBP) and tetranaphthoporphyrin (MTNP).…”

Section: Introductionmentioning

confidence: 99%

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Observation and Interpretation of Annulated Porphyrins: Studies on the Photophysical Properties ofmeso-Tetraphenylmetalloporphyrins

et al. 2003

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We present results of a joint computational and experimental study for a series of annulated metalloporphyrins in order to establish structure-property relationships. Specifically, we have examined the effects of substitution by meso-tetraphenylation, tetrabenzo and tetranaphtho annulation, and effects of changing the central metal from zinc (Zn) to palladium (Pd). Utilizing absorption and emission spectroscopy and laser flash photolysis techniques, the photophysical properties of these porphyrins have been determined. Upon the addition of benzo or naphtho groups, we observed an overall red shift in the ground state absorption spectra of both the B-bands and the Q-bands with increased conjugation and an increase in the Q-band to B-band intensity ratios. Time-dependent density functional theory calculations were performed on both series of porphyrins to identify the effects of phenyl, benzo, and naphtho substituents on the spectra. The benzo and naphtho adducts provide a larger contribution (typically 40-90%) to the observed red shifts due to increased π-conjugation, while there is a smaller contribution (typically 0-25%) from distortion of the porphyrin. Similarly, a red shift for the T 1 -T n absorption spectrum and an overall general broadening in the spectrum were found with increased conjugation. An increase in the triplet molar extinction coefficient through the near-infrared region with annulation was also found. Varying the metal has an effect on the overall absorption spectra; i.e., the ground state spectra of the Zn porphyrins are red-shifted relative to the Pd porphyrins. For the triplet excited state spectra there were small effects in the spectra by changing the metal with a significant contribution to the kinetic properties by the heavy atom effect of the Pd.

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Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Observation and Interpretation of Annulated Porphyrins: Studies on the Photophysical Properties ofmeso-Tetraphenylmetalloporphyrins

et al. 2003

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“…The π-expansion also induces strong π−π stacking between molecules, which results in low solubility of the porphyrins and difficulties in purification and derivatization. To overcome these obstacles, a few methods have been reported in the synthesis of TBPs and TNPs, ,,, e.g., an introduction of bulky substituents at the meso positions or peripheral aromatic rings, and an annealing of peripheral cyclohexyl structures to the aromatic rings in the presence of oxidants such as DDQ . However, these methodologies are not suitable for preparing TAnPs because TAnPs are less stable against oxidants compared to TNPs and TBPs, and only 5,10,15-tribiphenyl-ZnTAnP has been reported so far. , …”

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confidence: 99%