Optical Properties of Zinc(II) and Boron(III) Dipyrrinates with Different Structures

Nikonova, A. Yu.; Kuznetsova, R. T.; Aksenova, Iu. V.; Tel’minov, E. N.; Mayer, G. V.; Дудина, Н. А.; Nuraneeva, E. N.; Антина, Е. В.

doi:10.1134/s0030400x16030176

Cited by 14 publications

(7 citation statements)

References 13 publications

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“…However, this has not observed experimentally. 7,13,14,16,17 Instead, the opposite trend was observed when comparing di-iodine and dibromine-substituted compounds, where I 2 -tetraphenyl-aBDP exhibits a quite high quantum fluorescence of about γ = 0.33, whereas Br 2tetraphenyl-aBDP has almost negligible fluorescence with γ = 0.03 and Cl 2 -tetraphenyl-aBDP again appears to display a smaller rate of ISC, with γ = 0.28. These experimental results agreed well with the observed generation of photosensitized ( 1 O 2 ) by these molecules, where the most effective sensitization was not for the I 2 -substituted compound, having a triplet yield of 0.12, but rather for the Br 2 -substituted sensitizer (triplet yield of 0.83−0.89).…”

Section: ■ Introductionmentioning

confidence: 93%

“…However, this has not observed experimentally. 7,13,14,16,17 Instead, the opposite trend was observed when comparing di-iodine and di-bromine substituted compounds, where I 2 -tetraphenyl-aBDP exhibits a quite high quantum fluorescence of about γ=0.33, whereas Br 2 -tetraphenyl-aBDP has almost negligible fluorescence with γ=0.03 and Cl 2 -tetraphenyl-aBDP again appears to display a smaller rate of ISC, with γ=0.28.…”

Section: Introductionmentioning

confidence: 93%

“…9 Halogenated BDPs and in particular aBDPs were investigated quantitatively by spectroscopic measurements and by computation to analyze the fluorescence quenching by triplet sensitization. [7][8][9][10][11][12][13][14][15][16] Theoretically, a higher efficiency of S 1 T i transitions should be observed in the iodinated molecule (I-aBDP) than in brominated aBDP (Br-aBDP) due to stronger SOC and more efficient ISC for "gravity" effect of the heavier halogen congeners. However, this has not observed experimentally.…”

Section: Introductionmentioning

confidence: 99%

“…Halogenated BDPs and in particular a BDPs were investigated quantitatively by spectroscopic measurements and by computation to analyze the fluorescence quenching by triplet sensitization. − Theoretically, a higher efficiency of S 1 → T i transitions should be observed in the iodinated molecule (I- a BDP) than in the brominated a BDP (Br- a BDP) due to stronger SOC and more efficient ISC for a “gravity” effect of the heavier halogen congeners. However, this has not observed experimentally. ,,,, Instead, the opposite trend was observed when comparing di-iodine and dibromine-substituted compounds, where I 2 -tetraphenyl- a BDP exhibits a quite high quantum fluorescence of about γ = 0.33, whereas Br 2 -tetraphenyl- a BDP has almost negligible fluorescence with γ = 0.03 and Cl 2 -tetraphenyl- a BDP again appears to display a smaller rate of ISC, with γ = 0.28. These experimental results agreed well with the observed generation of photosensitized ( 1 O 2 ) by these molecules, where the most effective sensitization was not for the I 2 -substituted compound, having a triplet yield of 0.12, but rather for the Br 2 -substituted sensitizer (triplet yield of 0.83–0.89). , Previous computational work has not been able to explain this anomalous I/Br sensitization.…”

Section: Introductionmentioning

confidence: 99%

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Computational Investigation on the Photophysical Properties of Halogenated Tetraphenyl BODIPY

et al. 2020

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The electronic structure, transition probabilities and corresponding quantum yields of fluorescence in a family of dihalogen-tetraphenyl-aza-BODIPY were calculated at the Time-Dependent Density Functional and post-Hartree-Fock levels of theory. Excellent agreement between theoretical and experimental spectral-luminescent data was achieved with the HSE06 functional and the 6-311G* basis set. Since the fluorescence can be quenched through nonradiative intersystem spin crossing transitions from the lowest photoactive singlet state to triplet excited states, spin-orbit coupling matrix elements were calculated and applied along with Marcus-Levich-Jortner theory, leading to satisfactory agreement for the lifetimes in comparison with available experimental data. The anomalous dependence of the fluorescence efficiency on the atomic number of the halogen congeners was elucidated and shown to be due to an inversion between the fluorescent and the nearest triplet states in the iodinated compounds. The high rate of fluorescence quenching by intersystem crossings and the probability of collisions in a solvent between oxygen molecules and the molecules studied, shows that these molecules can provide efficient triplet sensitization. The most preferable sites for such interactions were predicted using electrostatic potential mapping at the extreme positive and negative charge points.

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Section: ■ Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Computational Investigation on the Photophysical Properties of Halogenated Tetraphenyl BODIPY

et al. 2020

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“…In this case, intramolecular electron transfer to form the CS state becomes competitive with the radiative decay from the S 1 state. The T 1 state in these zinc complexes is nonemissive at room temperature, but phosphorescence has been observed at 77 K. 33,34 The T 1 state has also been observed in room-temperature solution by transient absorption spectroscopy, 29,30 but to our knowledge, the yield of triplet state formation in these complexes has not been investigated. In our quest to design viable zinc-based photosensitizers, it is important to understand which factors influence ISC efficiency to rationally design chromophores with the highest possible triplet state yields.…”

Section: ■ Introductionmentioning

confidence: 94%

Quantifying Triplet State Formation in Zinc Dipyrrin Complexes

2019

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Photocatalysis is a promising method to harness solar energy and use it to form fuels and other high-value chemicals, but most sensitizers used in photocatalytic reactions are complexes of rare and expensive metals such as ruthenium and iridium. Zinc dipyrromethene complexes have potential to be a more earth-abundant alternative, but their photophysical properties are largely unexplored. In this study, triplet state formation was quantified in two zinc dipyrromethene complexes, with and without heavy atoms, by transient absorption spectroscopy. Without heavy atoms, the triplet quantum yield was 16% in toluene and 27% in THF. With the addition of heavy I atoms, the triplet quantum yield increased to 62−63% and was insensitive to solvent polarity. The fact that in the absence of heavy atoms the triplet yield is affected by solvent polarity and in the presence of heavy atoms it is not suggests that triplet formation occurs through different pathways in the two complexes. These triplet yields meet or exceed those of successful organic photosensitizers, illustrating the potential for zinc dipyrromethene complexes as photosensitizers.

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A New Sensitive and Selective Off-On Fluorescent Zn2+ Chemosensor Based on 3,3′,5,5′-Tetraphenylsubstituted Dipyrromethene

et al. 2016

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3,3',5,5'-Tetraphenyl-2,2'-dipyrromethene was described as a highly sensitive and selective Off-on fluorescent colorimetric chemosensor for Zn based on the chelation-enhanced fluorescence (CHEF) effect. The reaction of dipyrromethene ligand with Zn induces the formation of the [ZnL] complex, which exhibits the increasing fluorescence in 120 fold compared with ligand in the propanol-1/cyclohexane (1:30) binary mixture. The Zn detection limit was 1.4 × 10 М. The UV-Vis and fluorescence spectroscopic studies demonstrated that the dipyrromethene sensor was highly selective toward Zn cations over other metal ions (Na, Mg, Co, Ni, Fe, Cu, Mn, Cd and Pb), excluding Hg.

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Optical Properties of Zinc(II) and Boron(III) Dipyrrinates with Different Structures

Cited by 14 publications

References 13 publications

Computational Investigation on the Photophysical Properties of Halogenated Tetraphenyl BODIPY

Computational Investigation on the Photophysical Properties of Halogenated Tetraphenyl BODIPY

Quantifying Triplet State Formation in Zinc Dipyrrin Complexes

A New Sensitive and Selective Off-On Fluorescent Zn2+ Chemosensor Based on 3,3′,5,5′-Tetraphenylsubstituted Dipyrromethene

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