Bisanthra-thianthrene: synthesis, structure and oxidation properties

Yamashita, Masataka; Hayashi, Hironobu; Suzuki, Mitsuharu; Kuzuhara, Daiki; Yuasa, Junpei; Kawai, Tsuyoshi; Aratani, Naoki; Yamada, Hiroko

doi:10.1039/c6ra13036d

Cited by 12 publications

(4 citation statements)

References 26 publications

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“…To probe their redox activities, cyclic voltammograms (CVs) were performed on 1 a – 1 e (see Supporting Information and Figure 3b). The non‐protected 1 a exhibited two weak oxidation waves at 0.29 and 0.51 V (versus Fc/Fc + ), which were much less positive than those of a TA ( E 1/2 ox1 = 0.84 V and E 1/2 ox2 = 1.4 V), [29] indicating greatly increased electron density in the dithiin ring after fusion with pyrroles. Consequently, the radical cations of 1 a were extremely unstable and induced the broad CV spectrum even under super dry conditions.…”

Section: Resultsmentioning

confidence: 95%

Molecular Hinges by Fusion of Pyrrole and Dithiin: Synthesis, Structure, Redox Chemistry and Host–Guest Complexation of Dipyrrolo‐1,4‐dithiins

Liu

et al. 2023

Chemistry A European J

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A series of novel hinge‐like molecules, namely dipyrrolo‐1,4‐dithiins (PDs), were prepared and fully characterized by NMR, UV/vis, cyclic voltammogram, ESR, and single crystal X‐ray diffraction (SCXRD) analysis. The lateral fusion of pyrroles with 1,4‐dithiins has led to not only retained key features of a dithiin, but also enhanced redox‐activity with increased susceptibility to radical cations via redox or chemical oxidation. Stabilization of their radicals are observed for the N,N‐tert‐butyl or N,N‐triphenylmethyl PD as evidenced by ESR measurements. DFT calculations and SCXRD analysis revealed PDs are extremely flexible with adaptive molecular geometries that can be mechanically regulated via crystal packing or host–guest complexation. The excellent donor nature of PDs renders inclusion complexes with the cyclophane bluebox (cyclobis(paraquat‐p‐phenylene)), featuring association constants up to 104 M−1. Additionally, a planarized transition intermediate associated with inversion dynamics of a PD has been preserved in the pseudorotaxane structure with assistances of π⋅⋅⋅π and S⋅⋅⋅π interactions. The hinged structure, excellent redox‐activity, and adaptive nature of PDs could further enable accesses to exotic redox switchable host–guest chemistry and functional materials.

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Section: Resultsmentioning

confidence: 95%

Molecular Hinges by Fusion of Pyrrole and Dithiin: Synthesis, Structure, Redox Chemistry and Host–Guest Complexation of Dipyrrolo‐1,4‐dithiins

Liu

et al. 2023

Chemistry A European J

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“…This is consistent with a previous observation for the cation of 5,12diphenyltetracene derivatives, in which the cation shows the main absorption before 900 nm. 53,54 On consideration that the absorption feature of Tc •+ -Tc-Tc •+ (Tc •+ -Tc-Tc-Tc •+ ) is similar to that of Tc •+ -Tc-Tc (Tc •+ -Tc-Tc-Tc), no absorption signal from 900 to 1600 nm should be detected for Tc •+ -Tc-Tc •+ /Tc •+ -Tc-Tc-Tc •+ . These results make it difficult to distinguish the absorption feature of the tetracene cation from ns-TA spectra.…”

Section: Steady-state Absorption and Fluorescence Spectramentioning

confidence: 99%

Effects of the Separation Distance between Two Triplet States Produced from Intramolecular Singlet Fission on the Two-Electron-Transfer Process

Liu

Wang

et al. 2022

J. Am. Chem. Soc.

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To harvest two triplet excitons of singlet fission (SF) via a two-electron transfer efficiently, the revelation of the key factors that influence the two-electrontransfer process is necessary. Here, by using steady-state and transient absorption/ fluorescence spectroscopy, we investigated the two-electron-transfer process from the two triplet excitons of intramolecular SF (iSF) in a series of tetracene oligomers (dimer, trimer, and tetramer) with 7,7,8,8-tetracyanoquinodimethane (TCNQ) as an electron acceptor in solution. Quantitative two-electron transfer could be conducted for the trimer and tetramer, and the rate for the tetramer is faster than that for the trimer. However, the maximum efficiency of the two-electron transfer in the dimer is relatively low (∼47%). The calculation result of the free energy change (ΔG) of the secondelectron transfer for these three compounds (−0.024, −0.061, and −0.074 eV for the dimer, trimer, and tetramer, respectively) is consistent with the experimental observation. The much closer ΔG value to zero for the dimer should be responsible for its low efficiency of the two-electron transfer. Different ΔG values for these three oligomers are attributed to the different Coulomb repulsive energies between the two positive charges generated after the two-electron transfer that is caused by their various intertriplet distances. This result reveals for the first time the important effect of the Coulomb repulsive energy, which depends on the intertriplet distance, on the two-electron transfer process from the two triplet excitons of iSF.

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“…Original HRMS spectra for compounds 9, 24, S2, [15][16][17][18]21,23,24,25,28,30,32,34a,34b,and 38 (PDF) FAIR data, including the primary NMR FID files, for compounds 6, 9, 12−21, 23−25, 28, 30, 32−34, 37− 39, and…”

Section: * Sı Supporting Informationmentioning

confidence: 99%

“…Heating 28 in benzene at 90 °C afforded the dithiolcarbonate 30 predominantly in 72% yield via TS- 29 (path A), while the unexpected retro-Ene-type fragmentation occurred simultaneously to produce 2-alkenyl methyl sulfide 32 in 24% yield via TS- 31 (path B) . Exposing 30 to ethanolamine under air achieved the disulfide 33 , which was treated by P(NEt 2 ) 3 to smoothly furnish 32 , with the stereochemistry at C 18 maintained . The relative configurations of 30 , 32 , and 33 were established by extensive spectroscopic analysis including NOE analysis (see the Supporting Information for details).…”

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confidence: 99%

Synthetic Study Aiming at the Tricyclic Core of 12-epi-JBIR-23/24

Man

Zhou

et al. 2021

Org. Lett.

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The synthetic study toward highly enantio-and diastereoselective synthesis of the tricyclic framework of 12-epi-JBIR-23/24, a natural product analogue showing inhibitory activity against four malignant pleural mesothelioma cell lines, is presented herein. In this synthesis, a rhodium-catalyzed asymmetric three-component Michael/aldol reaction introduces three consecutive tertiary carbon centers, while the unique epoxyquinol core motif is successfully forged via [3,3]-sigmatropic rearrangement of an allylic xanthate, vinylogous Pummerer rearrangement, and a selective mesylation/epoxidation cascade of a triol.

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Bisanthra-thianthrene: synthesis, structure and oxidation properties

Abstract: A bis(tetracene radical cation) connected by a dithiin-ring is obtained by two-electron oxidation of bisanthra-thianthrene, instead of the dithianonacene dication.

Cited by 12 publications

References 26 publications

Molecular Hinges by Fusion of Pyrrole and Dithiin: Synthesis, Structure, Redox Chemistry and Host–Guest Complexation of Dipyrrolo‐1,4‐dithiins

Molecular Hinges by Fusion of Pyrrole and Dithiin: Synthesis, Structure, Redox Chemistry and Host–Guest Complexation of Dipyrrolo‐1,4‐dithiins

Effects of the Separation Distance between Two Triplet States Produced from Intramolecular Singlet Fission on the Two-Electron-Transfer Process

Synthetic Study Aiming at the Tricyclic Core of 12-epi-JBIR-23/24

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