5,5 '-bridged bis(1,2,3-dithiazoles): Spin states and charge-transfer chemistry
by Barclay, T. M.; Beer, L.; Cordes, A. W.; Oakley, R. T.; Preuss, K. E.; Reed, R. W.; Taylor, N. J.
Bifunctional 1,2,3-dithiazoles bridged with azine and phenylenediamine spacers have been prepared, with a view to determining the extent of communication between the two dithiazole rings as a function of the electronic and steric demands of the bridge. The crystal structure of the closed-shell diazine derivative [S2NClC2=NN=C2C-S-2] is rigorously planar. Cyclic voltammetry on this compound indicates two reversible one-electron oxidations. The radical cation state has been characterized by EPR spectroscopy and by crystal structure determination of its 1:1 PF6- salt. The latter reveals little interaction between neighboring radical cations; consistently, the material exhibits a conductivity of sigma < 10(-5) S cm(-1). Insertion of a phenylene group into the diazine bridge to afford [S2NClC2=NC6H4N=C2ClNS2] leads to significant torsional motion between the phenylene ring and the two end groups, as a result of which the two DTA rings are electronically independent; no radical cation state has been observed for this species. Crystal data for Cl2S4N4C4: a = 5.1469(15), b = 13.343(2), c;= 14.2031(17), orthorhombic, Pbca, Z = 4. Crystal data for Cl2S4N4C4PF6: a = 11.699(4), b = 12.753(5), c = 10.461(4), beta = 112.17(1)degrees monoclinic, C2/c, Z = 4. Crystal data for C12S4N4C10H4: a = 3.9477(6), b = 23.790(3), c = 7.3769(9), beta =90.793(12)degrees, monoclinic, P2(1)/c, Z = 2.
- Journal
- Inorganic Chemistry
- Volume
- 40
- Issue
- 12
- Year
- 2001
- Start Page
- 2709-2714
- URL
- https://dx.doi.org/10.1021/ic0010095
- ISBN/ISSN
- 1520-510X; 0020-1669
- DOI
- 10.1021/ic0010095