Phenyl substituted Mg porphyrazines: The effect of annulation of a chalcogen-containing heterocycle on the spectral-luminescent properties

Knyukshto, V. N.; Volkovich, D. I.; Гладков, Л. Л.; Kuzmitsky, V. A.; Ul-Haque, Anwar; Popkova, I. A.; Stuzhin, Pavel A.; Solovyov, K. N.

doi:10.1134/s0030400x12070119

Cited by 9 publications

(10 citation statements)

References 23 publications

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“…The dihedral angle between the phenyl ring plane and the macrocy cle plane (γ n ) is close to 45° (with a deviation of at most 3°). The changes in the bond lengths in the mac rocycle as a result of the addition of eight phenyl groups are similar to those observed for the MgTAP-MgPh 8 TAP pair [16]. The effect of the addition of phenyl groups on the bond lengths in the inner 16 membered ring is not strong.…”

Section: Quantum Chemical Calculationssupporting

confidence: 72%

“…This can be due to the change in molecular geometry in the transition to the first excited state S 1 ≡ Q x . This effect is not due to the rotation of phenyl groups, contrary to what was hypothesized in the same case for H 2 Ph 8 TAP [19] and MgPh 8 TAP [16], since it is also observed for molecules having no phenyl groups [4,20]. This effect takes place in various solvents; therefore, it is unlikely to arise from the solvation of pigment molecules.…”

Section: Condensed Matter Spectroscopy the Fluorescence And Electronimentioning

confidence: 53%

“…4. Comparison between the bond length data for H 2 P and the same data obtained by the same method for MgP [16] demonstrates that, as a S n '…”

Section: Quantum Chemical Calculationsmentioning

confidence: 76%

“…4). An increase in the degree of isolation of the С b -С b bonds takes place simultaneously, as in the case of the MgP-MgTAP pair of metal complexes [16]: the С b -С b bonds shorten, and the C а -C b bonds lengthen. There is a difference, however: the C a -N с bond lengths in H 2 P and H 2 TAP are almost equal.…”

Section: Quantum Chemical Calculationsmentioning

confidence: 98%

“…Molecular geometries were calculated by the DFT BPE/TZVP method implemented in a program pre sented by Laikov [13]. Its application to tetrapyrrole structures was reported earlier [14][15][16][17]. Excited elec tronic states of molecules were calculated by the INDO/Sm method [18] In this study, we had to record electronic spectra in toluene as well.…”

Section: Condensed Matter Spectroscopy the Fluorescence And Electronimentioning

confidence: 99%

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The fluorescence and electronic structure of phenyl-substituted tetraazachlorin molecules

et al. 2014

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The effect of the addition of phenyl groups to pyrrole rings of tetraazachlorins, a new class of tet rapyrroles, on the photophysical properties and electronic structure of the molecules has been investigated by a complex of experimental and theoretical methods. Characteristics of fluorescence at 293 and 77 K have been determined for phenyl substituted tetraazachlorins. The objects of this study include unsubstituted tet raazaporphine. The introduction of phenyl groups affords a marked increase in the fluorescence quantum yield. For tetraazaporphine and phenyl substituted tetraazachlorins, fluorescence buildup occurs as the tem perature is decreased from 293 to 77 K, but to a lesser extent than for tetraazachlorins having no phenyl groups, which were earlier studied by the authors. The fluorescence buildup mechanism is discussed. The sin glet oxygen generation quantum yield has been determined for the tetrapyrroles examined. This characteristic increases upon tetrapyrrole is phenylation. The electronic structure and absorption spectra of unsubstituted porphine and chlorin, tetraazaporphine, tetraazachlorin, octaphenyltetraazaporphine, and tetramethyl hexaphenyltetraazachlorin have been calculated by the INDO/Sm method (original modification of the INDO/S method) with molecular geometry optimization using DFT. The results of the quantum chemical calculation of the absorption spectra are in good agreement with experimental data for transitions to the low est excited electronic states Q x (S 1 ) and Q y (S 2 ).

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Section: Quantum Chemical Calculationssupporting

confidence: 72%

Section: Condensed Matter Spectroscopy the Fluorescence And Electronimentioning

confidence: 53%

“…4. Comparison between the bond length data for H 2 P and the same data obtained by the same method for MgP [16] demonstrates that, as a S n '…”

Section: Quantum Chemical Calculationsmentioning

confidence: 76%

Section: Quantum Chemical Calculationsmentioning

confidence: 98%

Section: Condensed Matter Spectroscopy the Fluorescence And Electronimentioning

confidence: 99%

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The fluorescence and electronic structure of phenyl-substituted tetraazachlorin molecules

et al. 2014

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1,2,5‐Chalcogenadiazole‐Annulated Tripyrazinoporphyrazines: Synthesis, Spectral Characteristics, and Influence of the Heavy Atom Effect on Their Photophysical Properties

Švec¹,

Zimčík²,

Nováková³

et al. 2014

Eur J Org Chem

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A series of low‐symmetry ZnII, MgII, and metal‐free porphyrazine derivatives with one 1,2,5‐chalcogenadiazole ring (with S, Se or Te) and three pyrazines bearing tert‐butylsulfanyls were synthesized. The absorption maxima of ZnII complexes lay at 660, 674, and 707 nm for S, Se, and Te, respectively, indicating increasing contribution of the 1,2,5‐chalcogenadiazole rings to the π‐electronic system. Photophysical studies revealed that introduction of Se as a chalcogen and ZnII as a central metal causes an increase in the singlet oxygen quantum yield, reaching a value of 0.81, whereas the combination of S and MgII gives only 0.39. This takes place on the account of the fluorescence quantum yields that differ significantly from 0.072 (ZnII+Se) to 0.51 (MgII+S). These results demonstrated the two‐dimensional heavy atom effect combining the role of the chalcogen (first dimension) as well as the central metal (second dimension). Attempts to prepare oxygen‐containing isologues led to the formation of an unexpected side product.

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Quantum-Chemical Calculations of the Geometric Structures and Electronic Spectra of Phthalocyanines MgPc and H2Pc and Their β-Octaphenyl Derivatives

et al. 2018

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Phenyl substituted Mg porphyrazines: The effect of annulation of a chalcogen-containing heterocycle on the spectral-luminescent properties

Cited by 9 publications

References 23 publications

The fluorescence and electronic structure of phenyl-substituted tetraazachlorin molecules

The fluorescence and electronic structure of phenyl-substituted tetraazachlorin molecules

1,2,5‐Chalcogenadiazole‐Annulated Tripyrazinoporphyrazines: Synthesis, Spectral Characteristics, and Influence of the Heavy Atom Effect on Their Photophysical Properties

Quantum-Chemical Calculations of the Geometric Structures and Electronic Spectra of Phthalocyanines MgPc and H2Pc and Their β-Octaphenyl Derivatives

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