Covalently Linked Porphyrin Dimers as Model Systems of the Photosynthetic Special Pair: Spectroscopy, Energetics and Photochemistry

Zenkevich, É. I.; Шульга, А. М.; Chernook, A. V.; Gurinovich, G. P.; Sagun, E. I.

doi:10.1007/978-1-4684-5991-3_35

Cited by 18 publications

(92 citation statements)

References 1 publication

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“…5-(10,15,20-Tris(p-hexylphenyl)-porphyrinyl)}benzene, (ZnHTPP) 2 . For the preparation of the dimer, we used the method developed for the synthesis of tetrameso-substituted porphyrins.…”

Section: 4-bis{[zinc(ii)]mentioning

confidence: 99%

“…The dimer fraction was boiled with zinc acetate in a chloroform-methanol mixture, evaporated, dissolved in benzene, and exposed to daylight until the absorption band of the chlorin admixture disappeared. 10 Following the chromatography on Al 2 O 3 (IV activity grade) with benzene, 32 mg (1%) of (ZnHTPP) 2 was obtained from crystallization in a chloroform-methanol mixture. UV-vis λ max (C 6 H 6 ), nm ( (10 3 M -1 ‚cm -1 )): 423 (564), 433 (682), 552 (50.8), 592 (14.9).…”

Section: 4-bis{[zinc(ii)]mentioning

confidence: 99%

“…We have already reported on the realization of such systems made up of Zn-tetraphenylporphyrin dimers (ZnTPP) 2 and dipyridyl-substituted free base porphyrins. 8 Two-fold coordination of the nitrogen atoms of the pyridyl substituents as axial extra-ligands to the central zinc ions of the Zn-porphyrin dimer subunits has been functionalized to form these complexes.…”

Section: Introductionmentioning

confidence: 99%

“…8 Two-fold coordination of the nitrogen atoms of the pyridyl substituents as axial extra-ligands to the central zinc ions of the Zn-porphyrin dimer subunits has been functionalized to form these complexes. The formation process has been followed by a change of absorption and fluorescence spectra of (ZnTPP) 2 in solution upon addition of the ligand. Complexation constants of up to 10 8 M -1 have been found in cyclohexane solutions at room temperature.…”

Section: Introductionmentioning

confidence: 99%

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Complexation and Interchromophoric Interactions in Self-Organized Porphyrin and Chlorin Triads

Chernook¹,

Shulga²,

Zenkevich³

et al. 1996

J. Phys. Chem.

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Spectral properties and equilibrium constants of multimolecular complexes (triads) formed by 2-fold coordination of dipyridyl-substituted free bases of porphyrin, chlorin, or tetrahydroporphyrin with Zn-porphyrin and Zn-chlorin dimers bridged by either of two different spacers between the monomeric entities have been studied in methylcyclohexane at room temperature. The ability of the dimers bridged by a -CH 2 -CH 2 -spacer to form complexes with the free bases is found to be much lower than that for the dimers with a phenyl spacer having complexation constants up to K C ) 5 × 10 7 M -1 . The complexation equilibrium is also affected strongly by the chemical nature of the free base and the position of the pyridyl substituents. Spectral effects occurring upon complexation in absorption spectra of the dimers are mainly due to ligation effects. Strong quenching of the dimer fluorescence in the complexes is attributed to effective singletsinglet energy transfer (ET) to the ligands.

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“…5-(10,15,20-Tris(p-hexylphenyl)-porphyrinyl)}benzene, (ZnHTPP) 2 . For the preparation of the dimer, we used the method developed for the synthesis of tetrameso-substituted porphyrins.…”

Section: 4-bis{[zinc(ii)]mentioning

confidence: 99%

Section: 4-bis{[zinc(ii)]mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Complexation and Interchromophoric Interactions in Self-Organized Porphyrin and Chlorin Triads

Chernook¹,

Shulga²,

Zenkevich³

et al. 1996

J. Phys. Chem.

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“…Up-to-date these phenomena have been investigated presumably for dimeric porphyrin assemblies [1,2] and for the ones with covalently linked electron donors or acceptors [3-51. More complex arrays have been studied to a less extent [6-81.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopy of interchromophoric interactions in self-organized porphyrin and chlorin complexes

Borczyskowski¹,

Rempel²,

Zenkevich³

et al. 1995

Journal of Molecular Structure

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Spectral-luminescentproperties of multimolecular complexes (triads and pentads, complexation constants range from 5.106 to 5.107 M") formed by two-fold coordination of dipyridyl and tetra-pyridyl substituted porphyrin or related molecules with Zn-porphyrin and Zn-chlorin dimers having various spacers between macrocycles (-CH2-CHz-or phenyl ring) have been studied in methylcyclohexane solutions in a temperature range from 140 to 360 K. The red shift of Zn-dimer electronic Q-and B-bands (AK550 cm-') upon complexation with pyridyl containing ligands is explained in terms of extra-ligation which influences the relative position for HOMO's al, and azu according to the four-orbital model. The splitting of Zndimer B-bands (AE2600 cm-') as well as the significant transformation of these bands in trimeric and pentameric complexes (redistribution of the absorption band intensities in Soret region and appearance of complicated splitted spectral manifolds A&1900 cm-') is connected with excitonic interactions of strong B-transitions of n-conjugated macrocycles included in the complex. Observed experimental splittings are compared with theoretical values calculated using the point dipole approximation and a computer-simulated geometry of the complexes under investigation. It has been observed that mutual influence of rc-electronic macrocycles in the complexes leads to the red shift of porphyrin extra-ligand free base Qbands (A~120 cm-') and is accompanied by quenching a fluorescence of certain components.

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Mechanisms of interchromophore interactions and relaxation of electron excitation energy in covalently bound porphyrin dimers

Gurinovich¹,

Zenkevich²,

Sagun³

et al. 1995

J Appl Spectrosc

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Covalently Linked Porphyrin Dimers as Model Systems of the Photosynthetic Special Pair: Spectroscopy, Energetics and Photochemistry

Cited by 18 publications

References 1 publication

Complexation and Interchromophoric Interactions in Self-Organized Porphyrin and Chlorin Triads

Complexation and Interchromophoric Interactions in Self-Organized Porphyrin and Chlorin Triads

Spectroscopy of interchromophoric interactions in self-organized porphyrin and chlorin complexes

Mechanisms of interchromophore interactions and relaxation of electron excitation energy in covalently bound porphyrin dimers

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