Deutsch
 
Hilfe Datenschutzhinweis Impressum
  DetailsucheBrowse

Datensatz

 
 
DownloadE-Mail
  (N-Methylthiocarbamoyl)tetrathiafulvalene derivatives and their radical cations: synthetic and X-ray structural studies

Moore, A. J., Bryce, M. R., Batsanov, A. S., Heaton, J. N., Lehmann, C. W., Howard, J. A. K., et al. (1998). (N-Methylthiocarbamoyl)tetrathiafulvalene derivatives and their radical cations: synthetic and X-ray structural studies. Journal of Materials Chemistry, 8, 1541-1550. doi:10.1039/A802037J.

Item is

Externe Referenzen

einblenden:

Urheber

einblenden:
ausblenden:
 Urheber:
Moore, A. J.1, Autor
Bryce, M. R.1, Autor
Batsanov, A. S.1, Autor
Heaton, J. N.1, Autor
Lehmann, C. W.1, 2, Autor           
Howard, J. A. K.1, Autor
Robertson, N.3, Autor
Underhill, A .E.3, Autor
Perepichka, I. F.4, Autor
Affiliations:
1Department of Chemistry, University of Durham, South Road, Durham, UK DH1 3L E, ou_persistent22              
2Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              
3Department of Chemistry, UCNW Bangor, Bangor, Gwynedd, UK L L 57 2UW, ou_persistent22              
4L . M. L itvinenko Institute of Physical Organic & Coal Chemistry, National Academy of Sciences of Ukraine, Donetsk 340114, Ukraine, ou_persistent22              

Inhalt

einblenden:
ausblenden:
Schlagwörter: -
 Zusammenfassung: Lithiation of 4,5-bis(methylsulfanyl)-TTF 9, 4,5-(ethylenedisulfanyl)-TTF 10, 4,5-dimethyl-TTF 11 and 4,5,5′-trimethyl-TTF 12 (TTF=tetrathiafulvalene) followed by reaction with methyl isothiocyanate affords the corresponding (N-methylthio-carbamoyl)-TTF derivatives 14–17, respectively, in 54–70% yields. These new TTF derivatives display a broad intramolecular charge-transfer band in their UV–VIS spectra arising from conjugation between the donor TTF ring and the acceptor N-methylthiocarbamoyl moiety. Steric hindrance between the adjacent N-methylthiocarbamoyl and methyl substituents in 17 causes a marked hyposchromic shift in this band (λmax 395 nm) compared to compounds 14–16 (Lambda max 435–467 nm). Consistent with the electron-withdrawing properties of the N-methylthiocarbamoyl substituent, its attachment to the TTF ring raises slightly the oxidation potential of the system. Charge transfer complexes of these donors and (N-methylthiocarbamoyl)-TTF 2 with 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) and salts with bromide anions are reported, some of which have high room temperature conductivity values. The X-ray crystal structures are presented for 16, 17 and the salts 2·Br, 14·TCNQ and (17)2·20. The structure of 16 comprises orthogonal dimers (kappa packing) while in the structure of 17 individual molecules are orthogonal to each other. There is weak intermolecular hydrogen bonding in both 16 and 17. In the structure of 2·Br, the radical cations 2+· are almost planar and they form an infinite stair-like stack of dimers, with bromide anions situated between the stacks, and linked with the cation by a strong N–H‥Br bond. The structure of 14·TCNQ comprises mixed ‥DDAADD‥ stacks; the N-methylthiocarbamoyl group engages in an interstack N–H‥N bond with a TCNQ anion. Analysis of the bond lengths in the structure suggests that there is partial charge transfer from 14 to TCNQ. In the structure of (17)2·20 molecules form mixed ‥DDADDA‥ stacks and analysis of bond lengths suggests that there is only a small degree of charge transfer from donor to acceptor. The geometries of compounds 2, 14, 16, 17 were optimised using the PM3 semi-empirical method and the results compare favourably with the X-ray structural data.

Details

einblenden:
ausblenden:
Sprache(n): eng - English
 Datum: 1998
 Publikationsstatus: Erschienen
 Seiten: -
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1039/A802037J
 Art des Abschluß: -

Veranstaltung

einblenden:

Entscheidung

einblenden:

Projektinformation

einblenden:

Quelle 1

einblenden:
ausblenden:
Titel: Journal of Materials Chemistry
Genre der Quelle: Zeitschrift
 Urheber:
Affiliations:
Ort, Verlag, Ausgabe: Cambridge, UK : Royal Society of Chemistry
Seiten: - Band / Heft: 8 Artikelnummer: - Start- / Endseite: 1541 - 1550 Identifikator: ISSN: 0959-9428
CoNE: https://pure.mpg.de/cone/journals/resource/954925273429