title: Reactivity of fluoro-substituted bis(thiocarbonyl) donors with diiodine: an XRD, FT-Raman, and DFT investigation.
abstract: The reactions of 1,3,8,10-tetrakis(4'-fluorophenyl)-4,5,6,7-tetrathiocino[1,2-b:3,4-b']diimidazolyl-2,9-dithione (4) and molecular diiodine afforded spoke adducts with stoichiometries 4·I2 and 4·3I2 , isolated in the compound 4·3I2·xCH2Cl2·(1-x)I2 (x=0.70), and characterized by single-crystal XRD and FT-Raman spectroscopy. The nature of the reaction products was investigated under the prism of theoretical calculations carried out at the DFT level. The structural data, FT-Raman spectroscopy, and quantum mechanical calculations agree in indicating that the introduction of fluorophenyl substituents results in a lowering of the Lewis basicity of this class of bis(thiocarbonyl) donors compared with alkyl-substituted tetrathiocino donors and fluorine allows for extended interactions that are responsible for solid-state crystal packing.
authors.affiliation: Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, Cagliari (Italy), Fax: (+39) 070-675-4456.
authors.forename: Annalisa
authors.initials: A
authors.lastname: Mancini
authors.forename: M Carla
authors.initials: MC
authors.lastname: Aragoni
authors.forename: Ann L
authors.initials: AL
authors.lastname: Bingham
authors.forename: Carlo
authors.initials: C
authors.lastname: Castellano
authors.forename: Susanne L
authors.initials: SL
authors.lastname: Coles
authors.forename: Francesco
authors.initials: F
authors.lastname: Demartin
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hursthouse
authors.forename: Francesco
authors.initials: F
authors.lastname: Isaia
authors.forename: Vito
authors.initials: V
authors.lastname: Lippolis
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Maninchedda
authors.forename: Anna
authors.initials: A
authors.lastname: Pintus
authors.forename: Massimiliano
authors.initials: M
authors.lastname: Arca
keywords: charge transfer; density functional calculations; fluorine; halogens; solid-state structures