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Chasing Self-Assembly of Thioether-Substituted Flavylium Salts in Solution and Bulk State.

ABSTRACT: Two series of flavylium triflates carrying alkoxy side chains in the A-ring (benzo unit of chromylium salt) and thioethers in the B ring (phenyl unit) (O_n -Fla-S_m ) as well as thioethers at both A and B ring (S_n -Fla-S_m ) were synthesized in order to understand the effect of thioether functionalization on their self-assembly and electronic properties. Concentration-dependent and diffusion ordered (DOSY) NMR experiments of O₁ -iV-Fla-S₃ indicate the formation of columnar H-aggregates in solution with antiparallel intracolumnar stacking of the AC unit (chromylium) of the flavylium triflate, in agreement with the solid state structure of O₁ -V-Fla-S₁ . Thioether substitution on the B ring changes the linear optical properties in solution, whereas it has no effect on the A ring. According to differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction bulk self-assembly of these ionic liquid crystals (ILCs) depends on the total number of side chains, yielding SmA and Lam_Col phases for ILCs with 2-3 chains and Col_ro , Col_h phases for ILCs with 3-6 chains. Thus, we demonstrated that thioethers are a useful design tool for ILCs with tailored properties.

SUBMITTER: Knoller JA

PROVIDER: S-EPMC9400860 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Chasing Self-Assembly of Thioether-Substituted Flavylium Salts in Solution and Bulk State.

Knöller Julius A JA Forschner Robert R Frey Wolfgang W Lang Johannes J Baro Angelika A Zens Anna A Molard Yann Y Giesselmann Frank F Claasen Birgit B Laschat Sabine S

Chemphyschem : a European journal of chemical physics and physical chemistry 20220517 13

Two series of flavylium triflates carrying alkoxy side chains in the A-ring (benzo unit of chromylium salt) and thioethers in the B ring (phenyl unit) (On -Fla-Sm ) as well as thioethers at both A and B ring (Sn -Fla-Sm ) were synthesized in order to understand the effect of thioether functionalization on their self-assembly and electronic properties. Concentration-dependent and diffusion ordered (DOSY) NMR experiments of O1 -iV-Fla-S3< ...[more]

PMID: 35446455

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Project description:Six new bio-inspired flavylium salts were synthesized and investigated by a combined computational and experimental study for dye-sensitized solar cell applications. The compounds were characterized by FT-IR, UV-Vis, NMR spectroscopy, and LC-MS spectrometry techniques. The pH-dependent photochromic properties of the flavylium dyes were investigated through a UV-Vis spectroscopy study and revealed that they follow the same network of chemical reactions as anthocyanins upon pH changes. The structural and electronic properties of the dyes were investigated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). Geometry optimization calculation revealed that all dyes, regardless of the specie, flavylium cations or quinoidal bases, present a planar geometry. The photovoltaic performances of the dyes, in both flavylium and quinoidal base forms, were evaluated by the HOMO and LUMO energies and by calculating the light-harvesting efficiencies, the free energy change of electron injection, and the free energy change regeneration. The MO analysis showed that all dyes can inject electrons into the conduction band of the TiO2 upon excitation and that the redox couple can regenerate the oxidized dyes. The results obtained for the free energy change of electron injection suggest that the quinoidal bases should inject electrons into the semiconductor more efficiently than the flavylium cations. The values for the free energy change regeneration showed that the redox electrolyte can easily regenerate all dyes. Dipole moment analysis was also performed. DSSCs based on the dyes, in both flavylium and quinoidal base forms, were assembled, and their photovoltaic performances were evaluated by measuring the open-circuit voltage, the short circuit current density, the fill factor, and the energy conversion efficiency. Results obtained by both experimental and computational studies showed that the overall performances of the DSSCs with the quinoidal forms were better than those obtained with the flavylium cations dyes.

Dataset Information

Chasing Self-Assembly of Thioether-Substituted Flavylium Salts in Solution and Bulk State.

Publications

Chasing Self-Assembly of Thioether-Substituted Flavylium Salts in Solution and Bulk State.

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