Dataset Information

Synthesis of 5,10-bis(Trifluoromethyl) Substituted ?-Octamethylporphyrins and Central-Metal-Dependent Solvolysis of Their meso-Trifluoromethyl Groups.

ABSTRACT: 5,10-Bistrifluoromethyl substituted ?-octamethylporphyrins were synthesized via a scrambling side reaction of a dipyrromethane precursor in the presence of a large excess of trifluoroacetic acid. Compared with the trans-analogs, the cis-analogs of meso-trifluoromethyl ?-octaalkylporphyrin showed more red-shifted absorption bands. These meso-trifluoromethyl derivatives of ?-octaalkylporphyrins underwent smooth metalation, similar to other common porphyrins, however, the corresponding zinc complexes underwent a type of solvolysis, whereby the trifluoromethyl groups were converted into methoxycarbonyl groups by the methanol used as solvent. UV-visible absorption spectra and X-ray crystal structure analyses revealed that the presence of a methoxycarbonyl substituent did not influence the deformation of the molecular framework and its absorption properties; this is because the methoxycarbonyl has a planar and perpendicular geometry, as opposed to the relatively bulky trifluoromethyl substituent.

SUBMITTER: Suzuki M

PROVIDER: S-EPMC6274281 | biostudies-other | 2016 Feb

REPOSITORIES: biostudies-other

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Publications

Synthesis of 5,10-bis(Trifluoromethyl) Substituted β-Octamethylporphyrins and Central-Metal-Dependent Solvolysis of Their meso-Trifluoromethyl Groups.

Suzuki Masaaki M Neya Saburo S Nishigaichi Yutaka Y

Molecules (Basel, Switzerland) 20160223 3

5,10-Bistrifluoromethyl substituted β-octamethylporphyrins were synthesized via a scrambling side reaction of a dipyrromethane precursor in the presence of a large excess of trifluoroacetic acid. Compared with the trans-analogs, the cis-analogs of meso-trifluoromethyl β-octaalkylporphyrin showed more red-shifted absorption bands. These meso-trifluoromethyl derivatives of β-octaalkylporphyrins underwent smooth metalation, similar to other common porphyrins, however, the corresponding zinc complex ...[more]

PMID: 26907247

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Project description:A series of tetrathiafulvalenes functionalized with one or two trifluoromethyl electron-withdrawing groups (EWG) is obtained by phosphite coupling involving CF3-substituted 1,3-dithiole-2-one derivatives. The relative effects of the EWG such as CF3, CO2Me and CN on the TTF core were investigated from a combination of structural, electrochemical, spectrochemical and theoretical investigations. Electrochemical data confirm the good correlations between the first oxidation potential of the TTF derivatives and the ?meta Hammet parameter, thus in the order CO2Me < CF3 < CN, indicating that, in any case, the mesomeric effect of the substituents is limited. Besides, crystal structure determinations show that the deformation of the unsymmetrically substituted dithiole rings, when bearing one, or two different EWG, and attributed to the mesomeric effect of ester or nitrile groups, is not notably modified or counter-balanced by the introduction of a neighboring trifluoromethyl group. DFT calculations confirm these observations and also show that the low energy HOMO-LUMO absorption band found in nitrile or ester-substituted TTFs is not found in TTF-CF3, where, as in TTF itself, the low energy absorption band is essentially attributable to a HOMO?LUMO + 1 transition. Despite relatively high oxidation potentials, these donor molecules with CF3 EWG can be involved in charge transfer complexes or cation radical salts, as reported here for the CF3-subsituted EDT-TTF donor molecule. A neutral charge transfer complex with TCNQ, (EDT-TTF-CF3)2(TCNQ) was isolated and characterized through alternated stacks of EDT-TTF-CF3 dimers and TCNQ in the solid state. A radical cation salt of EDT-TTF-CF3 is also obtained upon electrocrystallisation in the presence of the FeCl4 (-) anion. In this salt, formulated as (EDT-TTF-CF3)(FeCl4), the (EDT-TTF-CF3)(+•) radical cations are associated two-by-two into centrosymmetric dyads with a strong pairing of the radical species in a singlet state.

Dataset Information

Synthesis of 5,10-bis(Trifluoromethyl) Substituted ?-Octamethylporphyrins and Central-Metal-Dependent Solvolysis of Their meso-Trifluoromethyl Groups.

Publications

Synthesis of 5,10-bis(Trifluoromethyl) Substituted β-Octamethylporphyrins and Central-Metal-Dependent Solvolysis of Their meso-Trifluoromethyl Groups.

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