Heteropolyacene with Thianthrenium Ring Systems Proving<i>π</i>Electron Delocalization over S Atoms

Oyaizu, Kenichi; Matsubara, Ryohei; Iwasaki, Tomokazu; Tsuchida, Eishun

doi:10.1081/ma-120021417

Cited by 3 publications

(2 citation statements)

References 24 publications

(49 reference statements)

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“…Cyclisation of sulfoxide systems was also utilized in synthesis of oligomeric and polymeric systems containing other heteroatoms (X = O, N) in addition to sulfur. Starting from precursors ( 76 , 77 ), the corresponding dithianhtrene (9,10-dithia-anthracene), polyphenothiazine, as well as phenoxantine systems ( 78 , 79 ) with imine, ether, and thioether bridges, respectively, were obtained in good to excellent yields ( Scheme 15 ) [ 30 , 31 , 32 , 33 , 34 , 35 , 36 ].…”

Section: Cyclisation Of Sulfur Derivativesmentioning

confidence: 99%

The hetero-Friedel-Crafts-Bradsher Cyclizations with Formation of Ring Carbon-Heteroatom (P, S) Bonds, Leading to Organic Functional Materials

et al. 2020

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The interest in functional materials possessing improved properties led to development of new methods of their synthesis, which allowed to obtain new molecular arrangements with carbon and heteroatom motifs. Two of the classical reactions of versatile use are the Friedel-Crafts and the Bradsher reactions, which in the new heteroatomic versions allow to replace ring carbon atoms by heteroatoms. In the present work, we review methods of synthesis of C–S and C–P bonds utilizing thia- and phospha-Friedel-Crafts-Bradsher cyclizations. Single examples of C–As and lack of C–Se bond formation, involving two of the closest neighbors of P and S in the periodic table, have also been noted. Applications of the obtained π-conjugated molecules, mainly as semiconducting materials, flame retardants, and resins hardeners, designed on the basis of five- and six-membered cyclic molecules containing ring phosphorus and sulfur atoms, are also included. This comprehensive review covers literature up to August 2020.

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Section: Cyclisation Of Sulfur Derivativesmentioning

confidence: 99%

The hetero-Friedel-Crafts-Bradsher Cyclizations with Formation of Ring Carbon-Heteroatom (P, S) Bonds, Leading to Organic Functional Materials

et al. 2020

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“…π‐Conjugated porphyrin polymers have been employed in sensors,2–5 (electro)optical devices,6–8 and solar energy conversion systems 9–11. Coupling porphyrins as pendant groups to π‐conjugated backbones12–21 often result in physical distortions or changes in electronic density and thereby alters the properties of the backbone. Indeed, most of polythiophene derivatives containing porphyrin substituents are insulators with electrical conductivities of less than 10 −8 S/cm 22.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of a π‐conjugated hybrid of oligothiophene and porphyrin

Oyaizu

Hoshino

Ishikawa

et al. 2006

J. Polym. Sci. A Polym. Chem.

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5-(3-Thienyl)-10,15,20-triethyl-21H,23H-porphine (H 2 (ttep)) was synthesized and characterized. Oxidative polymerization of H 2 (ttep) gave a novel oligomeric porphyrin linked at the 2,5-positions of the thienyl group. Electric conductivity of 4 Â 10 À1 S/cm after I 2 doping indicated that the oligomer had a p-conjugated structure with a delocalization of p electrons over the thienylene backbone. PM3 calculations revealed a low HOCO-LUCO gap, which was consistent with the relatively high electric conductivity. Regioregular (head-to-tail) structure was inferred from spectroscopic and calculational results. The pendant porphyrin groups formed a regular J-type array along the thienylene backbone, which was indicated by a significant red shift of the Soret band maximum. Figure 6. (a) UV-vis spectra of H 2 (ttep) (3.5 Â 10 À7 mol/L) (solid curve) and undoped 1 (3.5 Â 10 À7 mol unit/L) (dotted curve) in DMSO. Optical path length was 1 cm. (b) UV-vis spectrum for the electropolymerized film of 1 on an ITO electrode. [Color figure can be viewed in the online issue, which is available at www.interscience. wiley.com.] 5410 OYAIZU ET AL.

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Electronic transport of benzothiophene-based chiral molecular solenoids studied by theoretical simulations

Tagami

Tsukada

Wada

et al. 2003

The Journal of Chemical Physics

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By the density-functional-derived tight-binding method, the electronic transport properties of two types of benzothiophene-based molecular wires, i.e., the linear and helical molecular wires have been investigated. In the molecular bridge system where these molecules are connected to the gold electrodes by S–Au bonds, the transmission peaks are found to lie at the energies somewhat lower than 0.5 eV below the Fermi level for both cases. Thus the conductances of both types of wires for the bias voltage less than 1.0 V are not so large without doping. Upon iodine doping, however, the new transmission peaks are found to appear around the Fermi level, particularly in the case of helical wires. It means that the conductances of the helical wires are expected to be improved dramatically by the chemical doping. Therefore, the doped helical molecular wires are predicted to work as molecular solenoids even under lower bias voltages. Next, the applicability of the current-induced magnetic field generated in such a molecular solenoid is considered. As an example, we propose a novel helical molecule where the hydrogen atoms connected to the inner C–C bonds of the helix are substituted by some kind of radicals. In this case the current-induced field can control the alignment of the radical spin orientations.

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Heteropolyacene with Thianthrenium Ring Systems ProvingπElectron Delocalization over S Atoms

Cited by 3 publications

References 24 publications

The hetero-Friedel-Crafts-Bradsher Cyclizations with Formation of Ring Carbon-Heteroatom (P, S) Bonds, Leading to Organic Functional Materials

The hetero-Friedel-Crafts-Bradsher Cyclizations with Formation of Ring Carbon-Heteroatom (P, S) Bonds, Leading to Organic Functional Materials

Synthesis and characterization of a π‐conjugated hybrid of oligothiophene and porphyrin

Electronic transport of benzothiophene-based chiral molecular solenoids studied by theoretical simulations

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