Two-photon absorption of tetraphenylporphin free base

Kruk, M. M.; Karotki, Aliaksandr; Drobizhev, Mikhail; Kuzmitsky, V. A.; Gael, V. I.; Rebane, Aleksander

doi:10.1016/s0022-2313(03)00096-6

Cited by 71 publications

(99 citation statements)

References 36 publications

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“…In addition, the importance of the lowest "gerade" states has recently been pointed out in the context of two-photon absorption of some porphyrin derivatives. [21] As can be seen from Table 1, the TDDFT and DFT/ MRCI methods predict the same order of the lowest four transitions of FBP. The first two, 1 B 3u and 1 B 2u , are optically allowed despite the very small oscillator strengths at the ground-state equilibrium geometry.…”

Section: Resultsmentioning

confidence: 66%

“…The obtained energies are in reasonable agreement with previously reported TDDFT and DFT/MRCI results. [17,18,[21][22][23] However, the calculated TDDFT energies of the T 1 and T 2 states now are considerably lower than the respective DFT/MRCI values. As a consequence, the DFT/MRCI method predicts significantly smaller energy distances between the lowest triplet and singlet excited states than does TDDFT.…”

Section: Resultsmentioning

confidence: 83%

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Singlet and Triplet Excited States and Intersystem Crossing in Free‐Base Porphyrin: TDDFT and DFT/MRCI Study

2008

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Extensive time-dependent DFT (TDDFT) and DFT/multireference configuration interaction (MRCI) calculations are performed on the singlet and triplet excited states of free-base porphyrin, with emphasis on intersystem crossing processes. The equilibrium geometries, as well as the vertical and adiabatic excitation energies of the lowest singlet and triplet excited states are determined. Single and double proton-transfer reactions in the first excited singlet state are explored. Harmonic vibrational frequencies are calculated at the equilibrium geometries of the ground state and of the lowest singlet and triplet excited states. Furthermore, spin-orbit coupling matrix elements of the lowest singlet and triplet states and their numerical derivatives with respect to nuclear displacements are computed. It is shown that opening of an unprotonated pyrrole ring as well as excited-state single and double proton transfer inside the porphyrin cavity lead to crossings of the potential energy curves of the lowest singlet and triplet excited states. It is also found that displacements along out-of-plane normal modes of the first excited singlet state cause a significant increase of the , , and spin-orbit coupling matrix elements. These phenomena lead to efficient radiationless deactivation of the lowest excited states of free-base porphyrin via intercombination conversion. In particular, the S1-->T1 population transfer is found to proceed at a rate of approximately 10(7) s(-1) in the isolated molecule.

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Section: Resultsmentioning

confidence: 66%

Section: Resultsmentioning

confidence: 83%

Singlet and Triplet Excited States and Intersystem Crossing in Free‐Base Porphyrin: TDDFT and DFT/MRCI Study

2008

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“…3(a)), which in turn is still less than the asymmetry of non-symmetrical isomers of H 2 TPP (where the 60 • twisting of phenyl rings causes a perturbation of otherwise centrosymmetric wavefunction of the tetrapyrrole ring). 40,41 Therefore, both H 2 TtBuPc and H 2 TBTAC can be considered as quasicentrosymmetrical, compared to stronger perturbed H 2 TPP and even non-centrosymetrical porphyrin no. 7 of Ref.…”

Section: Resultsmentioning

confidence: 99%

Alternative selection rules for one- and two-photon transitions in tribenzotetraazachlorin: Quasi-centrosymmetrical π-conjugation pathway of formally non-centrosymmetrical molecule

Makarov

Drobizhev

Wicks

et al. 2013

The Journal of Chemical Physics

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We compare the two-photon absorption (2PA) spectra of non-centrosymmetrical metal-free tribenzotetraazachlorin (H 2 TBTAC) and analogous symmetrical tetra-tert-butyl-phthalocyanine (H 2 TtBuPc). Surprisingly, despite formal lack of center of inversion, the 2PA spectrum of H 2 TBTAC displays a two-photon allowed transition at 935 nm, similar to gerade-gerade (g-g) transitions observed in H 2 TtBuPc and in other symmetrical phthalocyanines. This transition is even better resolved in the singlet-singlet excited-state absorption spectrum. We tentatively explain the survival of the g-g transition in H 2 TBTAC by assuming that the main π -electron conjugation pathway in the tetraazasubstituted tetrapyrrole macrocycle bypasses the outer parts of the two oppositely located isoindole rings and thus renders the optically responsive core of the chromophore quasi-centrosymmetrical. By using the independently measured ground-and excited-state absorption extinction coefficients, we also show that the two-photon absorptivity can be quantitatively explained by a simple threelevel model with the lowest energy Q 1 state serving as an intermediate level.

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“…To overcome this problem, one must operate in the biological transparent spectral range (700e1000 nm), wherein TPA is of course of great interest. However, the currently used systems (porphyrins and tetrapyrroles) are poor two-photon absorbers [54] and only very few examples can be found in the literature. First attempts relied on the use of the meso-substituted and water-soluble porphyrins with two-photon absorption cross-section (s TPA ) of the order 100 Göppert-Mayer (1 GM ¼ 10 À50 cm 4 s photon À1 molecule À1 ) in the near infrared [55].…”

Section: Singlet Dioxygen Generation For Photodynamic Therapy (Pdt) Omentioning

confidence: 99%

3MLCT excited states in Ru(II) complexes: Reactivity and related two-photon absorption applications in the near-infrared spectral range

Lemercier

Bonne

Four

et al. 2008

Comptes Rendus. Chimie

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This short review provides a concise summary of the current state of research on the population by two-photon absorption of the triplet metal-to-ligand RésuméCette courte revue a pour objectif de fournir un état de l'art actuel, le plus concis et précis possible, concernant la recherche sur le phénomène de population par absorption à deux photons de l'état excité triplet à transfert de charge 3 MLTC au sein de complexes du ruthénium(II). Outre les applications de ce phénomène d'optique non linéaire à la limitation optique dans le proche infrarouge, des applications plus particulières en biologie (imagerie, dosage tant in vitro que in vivo du dioxygène et thérapie photodynamique ou PDT) sont ici décrites et envisagées. Pour citer cet article : G. Lemercier et al., C. R. Chimie 11 (2008).

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Two-photon absorption of tetraphenylporphin free base

Cited by 71 publications

References 36 publications

Singlet and Triplet Excited States and Intersystem Crossing in Free‐Base Porphyrin: TDDFT and DFT/MRCI Study

Singlet and Triplet Excited States and Intersystem Crossing in Free‐Base Porphyrin: TDDFT and DFT/MRCI Study

Alternative selection rules for one- and two-photon transitions in tribenzotetraazachlorin: Quasi-centrosymmetrical π-conjugation pathway of formally non-centrosymmetrical molecule

3MLCT excited states in Ru(II) complexes: Reactivity and related two-photon absorption applications in the near-infrared spectral range

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