RESUMEN
The synthesis and detailed characterization of low-viscosity room-temperature ionic liquids (RTILs) and [BnPh3P]+ salts with the cyano(fluoro)borate anions [BF(CN)3]- (MFB), [BF2(CN)2]- (DFB), and [BF3(CN)]- as well as the new mixed-substituted anion [BFH(CN)2]- (FHB) is described. The RTILs with [EMIm]+ or [BMPL]+ as countercations were obtained in yields of up to 98% from readily available alkali metal salts and in high purities that allow application in electrochemical devices. Trends in thermal stability, melting and freezing behavior, density, electrochemical stability, dynamic viscosity, specific conductivity and ion diffusivity have been assessed and compared to those of the related tetracyanoborate- and cyano(hydrido)borate-RTILs. The crystal structure analysis of the [BnPh3P]+ salts of [BFn(CN)4-n]- (n = 0-4), [BHn(CN)4-n]- (n = 1-3) and [BFH(CN)2]- provided experimental access to anion volumina that together with ion molecular mass, electrostatic potential, shape and chemical stability have been correlated to physicochemical properties. In addition, the cytotoxicity of the [EMIm]+-ILs and potassium or sodium salts was studied.
RESUMEN
Narrow HOMO-LUMO gaps and high charge-carrier mobilities make larger acenes potentially high-efficient materials for organic electronic applications. The performance of such molecules was shown to significantly increase with increasing number of fused benzene rings. Bulk quantities, however, can only be obtained reliably for acenes up to heptacene. Theoretically, (oligo)acenes and (poly)acenes are predicted to have open-shell singlet biradical and polyradical ground states, respectively, for which experimental evidence is still scarce. We have now been able to dramatically lower the HOMO-LUMO gap of acenes without the necessity of unfavorable elongation of their conjugated πâ system, by incorporating two boron atoms into the anthracene skeleton. Stabilizing the boron centers with cyclic (alkyl)(amino)carbenes gives neutral 9,10-diboraanthracenes, which are shown to feature disjointed, open-shell singlet biradical ground states.
RESUMEN
Different types of high-yield, easily scalable syntheses for cyano(fluoro)borates Kt[BFn (CN)4-n ] (n=0-2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal-free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates. Boron trifluoride etherate, alkali metal salts, and trimethylsilyl cyanide selectively yield dicyanodifluoroborates or tricyanofluoroborates. Fluorination of cyanohydridoborates is the third reaction type that includes direct fluorination with, for example, elemental fluorine, stepwise halogenation/fluorination reactions, and electrochemical fluorination (ECF) according to the Simons process. In addition, fluorination of [BH(CN)2 {OC(O)Et}]- to result in [BF(CN)2 {OC(O)Et}]- is described.
RESUMEN
Salts of the tetrakis(pentafluoroethyl)aluminate anion [Al(C2 F5 )4 ]- were obtained from AlCl3 and LiC2 F5 . They were isolated with different counter-cations and characterized by NMR and vibrational spectroscopy and mass spectrometry. Degradation of the [Al(C2 F5 )4 ]- ion was found to proceed via 1,2-fluorine shifts and stepwise loss of CF(CF3 ) under formation of [(C2 F5 )4-n AlFn ]- (n=1-4) as assessed by NMR spectroscopy and mass spectrometry and supported by results of DFT calculations. In addition, the [(C2 F5 )AlF3 ]- ion was structurally characterized.
