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Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes.

ABSTRACT: Novel multistage redox tetrathiafulvalenes (TTFs) bearing 6-aryl-1,4-dithiafulvene moieties were synthesized by palladium-catalyzed direct C-H arylation. In the presence of a catalytic amount of Pd(OAc)₂, P(t-Bu₃)·HBF₄, and an excess of Cs₂CO₃, the C-H arylation of TTF with several aryl bromides bearing 1,3-dithiol-2-ylidenes took place efficiently to produce the corresponding ?-conjugated molecules. We also succeeded in the estimation of the oxidation potentials and number of electrons involved in each oxidation step of the obtained compounds by digital simulations.

SUBMITTER: Yoshimura A

PROVIDER: S-EPMC7237811 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes.

Yoshimura Aya A Kimura Hitoshi H Kagawa Kohei K Yoshioka Mayuka M Itou Toshiki T Vasu Dhananjayan D Shirahata Takashi T Yorimitsu Hideki H Misaki Yohji Y

Beilstein journal of organic chemistry 20200512

Novel multistage redox tetrathiafulvalenes (TTFs) bearing 6-aryl-1,4-dithiafulvene moieties were synthesized by palladium-catalyzed direct C-H arylation. In the presence of a catalytic amount of Pd(OAc)2, P(t-Bu3)·HBF4, and an excess of Cs2CO3, the C-H arylation of TTF with several aryl bromides bearing 1,3-dithiol-2-ylidenes took place efficiently to produce the corresponding π-conjugated molecules. We also succeeded in the estimatio ...[more]

PMID: 32509028

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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 and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes.

Publications

Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes.

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