Temperature dependence of Mg porphin, Cu porphin, and Pd porphin luminescence

Bohandy, J.; Kim, Boris F.

doi:10.1063/1.440093

Cited by 17 publications

(13 citation statements)

References 11 publications

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“…The matter is that the phosphorescence spectra of Cu porphyrins with a pronounced vibrational structure including the mentioned QLS of CuP phosphorescence [9,13] have been obtained so far for the cases when the lower levels 2 T 1 and 4 T 1 correspond to the electronic configuration 3 (1a 1u 4e g ) of the porphyrin ligand. Calculation [6,7] for this case yields DE DQ = 319 cm À1 , which agrees well with the given experimental values for CuP [9,10]. It is known from the theory of electronic spectra of porphyrins (see e.g.…”

Section: Resultssupporting

confidence: 86%

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Quasi-line phosphorescence spectra of the copper complex of meso-tetrapropylporphin at liquid helium temperature

Arabei

Solovyov

Egorova

2000

J. Porphyrins Phthalocyanines

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Quasi-line spectra of the 4 T 1→2 S 0 phosphorescence of Cu meso-tetrakis(n-propyl)porphin in n-octane at 4.2 K under wide-band and selective excitation have been obtained and analysed. A non-typically large distance between the edge components of the origin ‘multiplet’ (175 cm−1) indicating the sensitivity of the energy of the 0-0 transition of molecular impurity centres to the surroundings has been noted, which can lead to a significant inhomogeneous broadening in amorphous media. Two vibrations with frequencies of about 220 cm−1 are predominantly active in the phosphorescence spectrum. Unlike Cu porphin, the intensity of the corresponding quasi-lines is lower than the intensity of the 0-0 transition. From the broadening of the Q(0-0) band in the phosphorescence excitation spectrum at selective recording of the 0-0 quasi-line the lifetime of the level 2 S 1 (Q) has been determined as 35 fs.

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Section: Resultssupporting

confidence: 86%

“…Our data on CuTPrP can be commented on as follows. The preferred activity of two vibrations of frequencies of about 200 cm À1 agrees with the data for CuP [9,10]. The higher intensity of the 0-0 transition is possibly due to the more efficient spin-orbit interaction in the first order.…”

Section: Resultssupporting

confidence: 84%

Quasi-line phosphorescence spectra of the copper complex of meso-tetrapropylporphin at liquid helium temperature

Arabei

Solovyov

Egorova

2000

J. Porphyrins Phthalocyanines

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“…On the other hand, the luminescence emission at room temperature proceeds most likely via the 2 T→ 2 S 0 transition, where the tripdoublet state is reached via a thermal equilibrium, and its temperature dependence allows an estimation of the 2 T– 4 T separation. This was unambiguously shown for CuP by following the phosphorescence emission; a 267 cm –1 splitting was found there for the 2 T– 4 T splitting . The 2 S 0 → 2 T transition has a non-negligible oscillator strength, as measured through its absorption spectrum on the red edge of the 2 S 1 – 2 S 0 transition at ∼14700 cm –1 . , …”

Section: Discussionmentioning

confidence: 57%

“…This was unambiguously shown for CuP by following the phosphorescence emission; a 267 cm −1 splitting was found there for the 2 T− 4 T splitting. 32 The 2 S 0 → 2 T transition has a non-negligible oscillator strength, as measured through its absorption spectrum on the red edge of the 2 S 1 − 2 S 0 transition at ∼14700 cm −1 . 6,33 4.1.3.…”

Section: Discussionmentioning

confidence: 99%

An Efficient Indirect Mechanism for the Ultrafast Intersystem Crossing in Copper Porphyrins

et al. 2013

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The ultrafast dynamics of copper tetraphenylporphyrin (CuTPP), copper octaethylporphyrin (CuOEP), and of the free base tetraphenylporphyrin (H2TPP), excited in the S2 state have been investigated in the gas phase by femtosecond pump/probe experiments. The porphyrins were excited in the Soret band at 400 nm. Strikingly, the S2-S1 internal conversion in H2TPP is very rapid (110 fs), as compared to that of ZnTPP (600 fs), previously observed. In turn, CuTPP and CuOEP, excited in S2, follow an efficient and different relaxation pathway from that of other open-shell metalloporphyrins. These two molecules exhibit a sequential four-step decay ending on a slow evolution in the nanosecond range (2)S2 → (2)CT → (2)T → (2)Ground State. This latter evolution is linked to the formation of the (2)T, tripdoublet state in CuTPP, observed in the condensed phase. It is shown that an intermediate charge transfer state plays a crucial role in linking the porphyrin centered (1)ππ* and (3)ππ* configurations. A simple model is presented that allows a rapid evolution between these two configurations, via coupling of the porphyrin π system with the free d electron on the copper. The mechanism obviates the need for the spin orbit coupling within the porphyrin. The result is that these copper porphyrins can exhibit an ultrafast apparent intersystem crossing, unprecedented for organic molecules.

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“…Three of these are out-ofplane modes of a2 u symmetry, of which the mode of the lowest frequency (γ 9 ) is the doming motion of the complex. Detailed fluorescence and optical studies on various metallo porphines were reported by Bohandy and coworkers in the late seventies [83][84][85]. Further investigations of the phosphorescence on PdP in a matrix were carried out by A.…”

Section: Spectroscopic and Physical Propertiesmentioning

confidence: 99%

Porphyrin (porphine) — A neglected parent compound with potential

Senge

Davis

2010

J. Porphyrins Phthalocyanines

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ABSTRACT:Porphine is the parent compound of a family of biologically and chemically relevant compounds called porphyrins. The potential of these compounds is enormous and it would be advantageous to use the porphine (porphyrin) unit as a building block for the synthesis of diverse porphyrin complexes with a wide range of applications. However, despite first being synthesised over seventy years ago, porphine has not been utilized to its full extent due to low yield syntheses and poor solubility. Recent advances have now overcome many of these problems. The purpose of this review is to illustrate the advances made in porphine chemistry to illustrate the inherent potential of this simple compound. KEYWORDS:Porphine, porphyrin, metalloporphyrin, tetrapyrroles.

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Temperature dependence of Mg porphin, Cu porphin, and Pd porphin luminescence

Cited by 17 publications

References 11 publications

Quasi-line phosphorescence spectra of the copper complex of meso-tetrapropylporphin at liquid helium temperature

Quasi-line phosphorescence spectra of the copper complex of meso-tetrapropylporphin at liquid helium temperature

An Efficient Indirect Mechanism for the Ultrafast Intersystem Crossing in Copper Porphyrins

Porphyrin (porphine) — A neglected parent compound with potential

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