Synthesis and Investigation of the Effect of Substitution on the Structure, Physical Properties, and Electrochemical Properties of Anthracenodifuran Derivatives

Abstract

A series of syn/anti mixtures of anthradifuran (ADF) and substituent compounds were systematically synthesized, and the effect of substitution at the 5,11-positions on the neutral and radical states of ADF was investigated. All compounds were measured and analyzed by absorption and fluorescence spectroscopy, cyclic voltammetry, electrochemical absorption spectroscopy, and DFT calculations. The absorption spectra of 5,11-substituent compounds in their neutral state were red-shifted. In addition, the substituted compounds exhibited increased thermal stability with respect to the parent 1a because of elongation of the π-conjugation and an increased steric hindrance effect due to the bulky ethynyl substituent groups. The cyclic voltammograms of all of the compounds exhibited irreversible reduction potentials and irreversible oxidation potentials, except in the case of (trimethylsilyl)silylethynyl-substituted ADF. When the materials were subjected to oxidation/reduction potentials, the radical cation and anion species were generated. The absorption spectra of the radical-cation species of the compounds exhibited similar characteristics and similar absorption ranges (550-1400 nm), whereas the spectra of the radical anion species were blue-shifted (550-850 nm) compared than that of the parent 1a(•-) (550-1100 nm). The DFT computation results suggested that the radical states of lowest energy transitions occurred primarily from π to π(SOMO) or from π(SOMO) to π*.

Interaction of SrO-terminated SrTiO3 surface with oxygen, carbon dioxide, and water

“…In recent years, the advance of carbon neutral energy technologies has been a driving force for the active research in energy related materials for applications in fuel cells, 1 solar cells, 2 artificial photosynthesis devices, [3][4][5][6][7] high capacity Li-ion batteries, 8 etc. Amongst those technologies, particular interest has been devoted to solid oxide fuel cells (SOFC) due to their remarkable ability to operate with various fuels, i.e., hydrogen, methane, methanol, as electricity generating devices (fuel cells) or as fuel generating devices (electrolyzers).…”

Photocatalytic Water Splitting on KTa(Zr)O3 Modified with Acene-Based Organic Semiconductors

“…Various acene-based dyes, that is, TIPS-PEN, 5,11-bis-((trimethylsilyl)-ethynyl)anthradifuran (TMS-ADF), 5,11-bis-((triethylsilyl)ethynyl)anthradifuran (TES-ADF), 5,11-bis-(triisopropylsilylethynyl)anthradifuran (TIPS-ADF), 5,11-bis-(tris-(trimethylsilyl)silylethynyl)anthradifuran (TTMSS-ADF), and 5,11-bis((phynyl)-ethynyl)anthradifuran (Ph-ADF), were synthesized as previously reported. 33 Figure 1 shows the molecular structures of these dyes. The dye modification of KTa(Zr)O 3 was performed according to an evaporation-todryness method using pyridine as the solvent under dark condition.…”