过程材料6-外文文献.doc

Activation of Hydrogen- and Halogen-Bonding Interactions in Tetrathiafulvalene-Based Crystalline Molecular Conductors 4.3. Radical Cation Salts of Halogenated Tetrathiafulvalenes 4.3.1. C-Hal...Halanion Interactions 4.3.2. C-Hal...O,Sanion Interactions 4.3.3. C-Hal...N Interactions 4.3.4. Evolution of Halogen Bonding in TTF Salts 4.4. Halogen Bonding Interactions in the Anionic Network 5. Concluding Remarks 6. Acknowledgments 4.3. Radical Cation Salts of Halogenated Tetrathiafulvalenes A distinction will be made among the various salts of halogenated tetrathiafulvalenes between (i) those incorporating halogenated anions (Br-, IBr2-, I3-),where Hal...Halanion interactions were expected, and (ii) those incorporating other heteroatoms as Lewis bases for Hal...B interactions, essentially organic and inorganic nitriles where Hal...N≡C interactions were anticipated. 4.3.1. C-Hal...Halanion Interactions Crystals of neutral, chlorinated tetrathiafulvalenes exhibit at best close-packed Cl...Cl interactions.Because of the strong electronegative character of the chlorine atom, Cl-substituted TTFs oxidize at higher potentials than the bromo or iodo derivatives151 and their radical cation salts have not been investigated to any extent. A 2:1 salt of EDT-TTFCl2 has been obtained by chemical oxidation with the strong TCNQF4 oxidant,152 while electrocrystallization experiments afforded a 1:1 salt with ClO4-, (EDT-TTFCl2)-(ClO4), and with EDO-TTFCl2 and (n-Bu4NPF6), a 2:1salt formulated as (EDO-TTFCl2)2(PF6) was obtained.153 Short type I Cl...Cl contacts were onlyobserved in (EDT-TTFCl2)2(TCNQF4) with Cl...Cl =3.42 ? andθ1=θ2 =126°. Note also that a shorter type I contact (3.38 ? ,θ1=θ2 = 146°) was observed in neutral EDO-TTFCl2.145 On the other hand, several salts of o-dibromotetrathiafulvalene derivatives have been synthesized, essentially with inorganic polyhalides such as I3- or IBr2- with the objective to promote cation...anion, Br...Br, or Br...I interactions. And ind