Effect of peripheral substitution on electron and energy transfer in electrostatically bound zinc-magnesium porphyrin dimers

Journal Article · Thu May 23 04:00:00 EDT 1996 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/jp9603290· OSTI ID:263209

Berg, A; Rachamim, M; Galili, T; Levanon, H ^[1]

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1. Hebrew Univ. of Jerusalem (Israel)

We report on intramolecular electron and/or energy transfer (IET and IEnT), in two photoexcited electrostatically bound dimers: (1) zinc(II) tetrakis(4-sulfonatophenyl)porphyrin and magnesium(II) tetrakis(4-N,N,N-trimethylanilinium)porphyrin, [ZnTSPP-MgTTAP]; and (2) zinc(II) tetrakis(4-N,N,N-trimethylanilinium)porphyrin and magnesium(II) tetrakis(4-sulfonatophenyl)porphyrin, [ZnTTAP-MgTSPP]. The photochemical properties of both dimers, dissolved in dimethylsulfoxide-glycerol (DMSO-Glyc, 140 K), were investigated by continuous wave time-resolved electron paramagnetic resonance (CW-TREPR) spectroscopy. It is demonstrated that by changing the peripheral substitution of the particular metalloporphyrin in the dimer, an IET route, parallel to the singlet IEnT, can be triggered. Thus, singlet IEnT from the Zn to the Mg constituent is the only process in [ZnTSPP-MgTTAP], while IET to produce a charge-separated state, [ZnTTAP{sup .+}-MgTSPP{sup .-}] accompanies the IEnT in [ZnTTAP-MgTSPP]. 42 refs., 7 figs., 1 tab.

• OSTI ID: 263209
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 21 Vol. 100; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
DIMERS
ELECTRON SPECTRA
ELECTRON SPIN RESONANCE
ELECTRON TRANSFER
ENERGY TRANSFER
MAGNESIUM COMPLEXES
PHOTOCHEMICAL REACTIONS
PORPHYRINS
ZINC COMPLEXES