Red-shifted emission spectra of several meso-substituted copper porphyrins in fluid solution

Asano-Someda, Motoko; Kaizu, Youkoh

doi:10.1016/1010-6030(94)03966-x

Cited by 28 publications

(45 citation statements)

References 52 publications

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“…The phosphorescence spectra of Cu tetrakis(o-tolyl)porphin and CuTMP in frozen rigid glass solutions proved to be similar to the spectrum of CuTPrP. The data of Refs [3,5] on the phosphorescence spectra of CuTPrP and CuTMP at 77 K are in qualitative agreement. In Ref.…”

Section: Introductionsupporting

confidence: 57%

“…Refs [18,19]) that the two lower triplet levels of a metalloporphyrin molecule have close energies and correspond to practically pure configurations 3 (1a 1u 4e g ) and 3 (3a 2u 4e g ). There are various and substantial reasons to consider that in metal complexes of meso-tetraarylporphyrins and mesotetraalkylporphyrins, in particular, in copper complexes as well, the T 1 state of the macrocycle has the configuration 3 (3a 2u 4e g ) [1][2][3][4][5][6][7][20][21][22]. As an example, we give the data [20] that a typical picture of thermally activated phosphorescence absent in CuTPP appears when five atoms of fluorine that decrease the energy of the orbital 3a 2u are introduced in each phenyl ring of a CuTPP molecule.…”

Section: Resultsmentioning

confidence: 99%

“…It is known that the copper complexes of meso-substituted porphyrins (these are primarily Cu tetraphenylporphin (CuTPP) [1,2], Cu tetramesitylporphin (CuTMP) [3], Cu tetrakis(n-propyl)porphin (CuTPrP) [3], etc.) have phosphorescence spectra that are non-typical of metalloporphyrins at 77 K. As compared with Cu porphyrins substituted at the b positions of pyrrole rings (see e.g.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, the bands of phosphorescence spectra are more diffuse, especially for CuTPP [1,2], although the indications of the vibrational structure do persist. An intense short-wavelength band that is accompanied either by a pronounced intense band on the long-wavelength slope as in the case of CuTPrP and CuTMP [3] or by an inflection as in the case of CuTPP [3] deserves special attention. This superposition of the bands makes it impossible, at liquid nitrogen temperature, to unambiguously solve the problem of localization of transitions that manifest themselves in the phosphorescence spectra.…”

Section: Introductionmentioning

confidence: 99%

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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: Introductionsupporting

confidence: 57%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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“…It is worth noting the resemblance of this picture to a vibronic distortion of emissive states in copper(II) porphyrins. 65,66 In the case of pronounced JT effects as in CuCl 4…”

Section: Resultsmentioning

confidence: 99%

Probing the Fate of Lowest-Energy Near-Infrared Metal-Centered Electronic Excited States: CuCl₄^2–and IrBr₆^2–

et al. 2015

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Ultrafast transient absorption spectroscopy is used to investigate the radiationless relaxation dynamics of CuCl4(2-) and IrBr6(2-) complexes directly promoted into their lowest-energy excited metal-centered states upon near-infrared femtosecond excitation at 2000 nm. Both the excited CuCl4(2-) (2)E and IrBr6(2-) (2)Ug'(T2g) states undergo internal conversion to the ground electronic states, yet with significantly different lifetimes (55 fs and 360 ps, respectively) despite the fact that the (2)E and (2)Ug'(T2g) states are separated by the same energy gap (∼5000 cm(-1)) from the respective ground state. This difference likely arises from the predominance of the Jahn-Teller effect in a Cu(2+) ion and the spin-orbit coupling effect in an Ir(4+) ion. The approach documented in this work may be used for elucidating the role of low-energy metal-centered states in relaxation cascades of a number of coordination compounds, allowing for design of efficient light-triggered metal complexes.

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Photoacoustic Measurements of Porphyrin Triplet-State Quantum Yields and Singlet-Oxygen Efficiencies

et al. 1998

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Photoacoustic calorimetry was used to measure the quantum yields of singlet molecular oxygen production by the triplet states of tetraphenylporphyrin (TPP), ZnÀTPP and CuÀTPP in toluene, yielding values of 0.67 AE 0.14, 0.68 AE 0.19 and 0.03 AE 0.01, respectively. We show that a novel dichlorophenyl derivative of Zn À TPP is capable of singlet-oxygen production with a 0.90 AE 0.07 quantum yield. The synthesis and characterisation of a new photostable chlorin with high absorptivity in the red that is capable of singlet-oxygen production with 0.54 AE 0.06 quantum yield is described. Our results suggest that chlorinated chlorins may be interesting new sensitisers for photodynamic therapy.

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Red-shifted emission spectra of several meso-substituted copper porphyrins in fluid solution

Cited by 28 publications

References 52 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

Probing the Fate of Lowest-Energy Near-Infrared Metal-Centered Electronic Excited States: CuCl₄^2–and IrBr₆^2–

Photoacoustic Measurements of Porphyrin Triplet-State Quantum Yields and Singlet-Oxygen Efficiencies

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Red-shifted emission spectra of several meso-substituted copper porphyrins in fluid solution

Cited by 28 publications

References 52 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

Probing the Fate of Lowest-Energy Near-Infrared Metal-Centered Electronic Excited States: CuCl42–and IrBr62–

Photoacoustic Measurements of Porphyrin Triplet-State Quantum Yields and Singlet-Oxygen Efficiencies

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Probing the Fate of Lowest-Energy Near-Infrared Metal-Centered Electronic Excited States: CuCl₄^2–and IrBr₆^2–