TY - JOUR
T1 - C603- versus C604- /C 602- - Synthesis and characterization of five salts containing discrete fullerene anions
AU - Boeddinghaus, M. Bele
AU - Klein, Wilhelm
AU - Wahl, Bernhard
AU - Jakes, Peter
AU - Eichel, Rüdiger A.
AU - Fässler, Thomas F.
PY - 2014/4
Y1 - 2014/4
N2 - Five new compounds, [Rb(18crown-6)]3[C60] (1), [Rb(18crown-6)]6[C60]2(C3H 7NO)2(C4H8O)2 (2), [Rb(benzo18crown-6)]6[C60]2(C2H 8N2)5 (3), [Cs(benzo18crown-6)] 3C60(C2H8N2)2 (4), and [Cs3(benzo18crown-6)5]C60(C 2H8N2)(4.5+x) (5) were synthesized and characterized by single-crystal X-ray structure determination. All compounds contain discrete C60 anions, which are ordered in 1, 2, and 4, where direct cation-anion contacts occur. The unit cells of 1 and 2 contain two independent fullerides, which coordinate to the rubidium atoms either of two or of four [Rb(18crown-6)] units. Owing to the presence of differently coordinated fullerene units in compounds 1 and 2, a possible disproportionation of C 603- into C602- and C 604- anions is discussed. In 3 and 4 the C60 anions are coordinated by three Rb and Cs atoms, respectively. In all compounds the average charge of the anion is -3. Magnetic data reveal a doublet spin state for 3. The EPR spectra are discussed for compounds 3 and 5. The role of a dynamic Jahn-Teller distortion is discussed, and we report the first IR spectroscopic data of fullerene trianions, which have been obtained in solution.
AB - Five new compounds, [Rb(18crown-6)]3[C60] (1), [Rb(18crown-6)]6[C60]2(C3H 7NO)2(C4H8O)2 (2), [Rb(benzo18crown-6)]6[C60]2(C2H 8N2)5 (3), [Cs(benzo18crown-6)] 3C60(C2H8N2)2 (4), and [Cs3(benzo18crown-6)5]C60(C 2H8N2)(4.5+x) (5) were synthesized and characterized by single-crystal X-ray structure determination. All compounds contain discrete C60 anions, which are ordered in 1, 2, and 4, where direct cation-anion contacts occur. The unit cells of 1 and 2 contain two independent fullerides, which coordinate to the rubidium atoms either of two or of four [Rb(18crown-6)] units. Owing to the presence of differently coordinated fullerene units in compounds 1 and 2, a possible disproportionation of C 603- into C602- and C 604- anions is discussed. In 3 and 4 the C60 anions are coordinated by three Rb and Cs atoms, respectively. In all compounds the average charge of the anion is -3. Magnetic data reveal a doublet spin state for 3. The EPR spectra are discussed for compounds 3 and 5. The role of a dynamic Jahn-Teller distortion is discussed, and we report the first IR spectroscopic data of fullerene trianions, which have been obtained in solution.
KW - Crystal structure determination
KW - Fullerenes
KW - Jahn-Teller effect
KW - Magnetic properties
KW - Polyanions
UR - http://www.scopus.com/inward/record.url?scp=84897562872&partnerID=8YFLogxK
U2 - 10.1002/zaac.201300607
DO - 10.1002/zaac.201300607
M3 - Article
AN - SCOPUS:84897562872
SN - 0044-2313
VL - 640
SP - 701
EP - 712
JO - Zeitschrift fur Anorganische und Allgemeine Chemie
JF - Zeitschrift fur Anorganische und Allgemeine Chemie
IS - 5
ER -