This journal is © The Royal Society of Chemistry 2000
Supplemental Information (for electronic deposition) manuscript no. a907535f
"Vanadium [Dicyanoperfluorostilbene]2•yTHF: A Molecule-Based Magnet with Tc ~ 205 K",
Jeffrey P. Fitzgerald, Bharat B. Kaul and Gordon T. Yee
Experimental
Elemental analyses were performed by Desert Analytics, Tucson, AZ. Magnetic measurements
were performed on a Quantum Design MPMS-5S SQUID magnetometer. Cyclic voltammetry
experiments were done in dry acetonitrile with 0.1 M tetrabutylammonium hexafluorophosphate
as supporting electrolyte. Analyte concentration was 510-3 M. The reference electrode used was
a silver wire in 0.01 M AgNO3 in acetonitrile. Ferrocene was added as an internal standard
reference. Scan rate was 200 mV/sec.
Procedure for preparation of ,'-dicyanoperfluorostilbene:
A solution of potassium tert-butoxide (5.42 g, 0.048 mol), dissolved in 10 mL of dry THF, was
added dropwise over 40 min to solution of I2 (6.12 g, 0.024 mol) and
pentafluorophenylacetonitrile (5.0 g, 0.024 mol) in 45 mL of THF maintained at 0 C. The
reaction mixture quickly darkened and eventually turned a deep blue-green. The mixture was
allowed to warm to room temperature as it stirred overnight. Workup consisted of removal the
bulk of the THF solvent on a rotary evaporator, dissolving the resulting slurry in water and
extracting with diethyl ether. The combined ether layers were dried with aqueous brine and then
reduced on a rotary evaporator. The resulting oil was adsorbed onto SiO2 and loaded onto a SiO2
flash column that was eluted initially with hexanes, increasing gradually in polarity to 2:1
hexanes/ dichloromethane. The trans isomer was eluted from the column first (4:1
hexanes/dichloromethane) followed by the cis isomer. Removal of solvent and recrystallization of
the resulting solids from benzene and hexanes, respectively, gave crystals of the desired
This journal is © The Royal Society of Chemistry 2000
compounds, 1.11 g (22%) of the trans isomer (m.p. = 171-173 C) as white flakes and 0.65 g
(13%) of the cis isomer (m.p. = 149-151 C) as white needles. Spectroscopic data for transDCPFS: Anal. Calcd for C16F10N2: C, 46.85; F, 46.32; N, 6.83. Found: C, 46.90; F, 46.42; N,
6.66. MS: m/e = 410, 391, 365, 360, 341, 310, 217. IR (KBr): (cm-1) 2228, 1648, 1508, 1438,
1334, 1102, 1059, 1000, 960. 19F NMR (CDCl3): (ppm vs. C6F6): 26.91 (d, 2F), 17.78 (t, 1F),
4.53 (t, 2F) ppm vs. C6F6. 13C NMR (CDCl3):  (ppm vs 13CDCl3) 136-147 (m, aromatic C's
bearing F), 119.84 (s, alkene C), 111.97 (s, nitrile C), 105.34 (t, aromatic C attached to double
bond). Spectroscopic data for cis-DCPFS: Anal. Calcd for C16F10N2: C, 46.85; F, 46.32; N, 6.83.
Found: C, 46.74; F, 46.74; N, 6.99. MS: m/e = 410, 391, 365, 360, 341, 310, 217. IR (KBr):
(cm-1) 2230, 1648, 1508, 1438, 1336, 1164, 1102, 1047, 1000, 961, 813. 19F NMR (CDCl3): 
(ppm vs. C6F6): 30.83 (d, 2F), 23.23 (t, 1F), 10.10 (t, 2F). 13C NMR (CDCl3)  (ppm vs 13CDCl3)
= 136-147 (m, aromatic C's bearing F), 119.64 (s, alkene C), 112.39 (s, nitrile C), 105.05 (t,
aromatic C attached to double bond).
Procedure for preparation of V(DCPFS)2•yTHF:
Preparation of V(DCPFS)2•yTHF was carried out utilizing standard techniques in a nitrogen-filled
Braun glove box maintained at less than 5 ppm O2. [V(CO)6] was synthesized by a previously
published method. See J. E. Ellis, R. A. Faltynek, L. Rochfort, R. E. Stevens, G. A. Zank, Inorg.
Chem. 1980, 19, 1082-1085. Vanadium hexacarbonyl (23 mg, 1.010-4 mol), was dissolved in 3
mL THF (evolution of gas presumed to be carbon monoxide was observed). To this was added a
solution of DCPFS (94 mg, 2.310-4 mol) in 7 mL THF. The color of the solution turned reddish
purple. After 1 h of stirring the reaction mixture was deep purple in color and there was some
dark solid present. The solvent was removed in vacuo. The residue was triturated under 7 mL
ether for 15 min, filtered, washed with ether until the filtrates run clear, (approx. 10 mL) and
dried in vacuo. Yield: 63 mg (60%). Anal. Calcd. for V(DCPFS)2•2THF (C40H16F20N4O2V): C,
This journal is © The Royal Society of Chemistry 2000
47.31; H, 1.59; F, 37.42; N, 5.52; V, 5.02. found (average of five analyses): C, 45.84; H, 1.49; F,
29.74; N, 5.05; V, 6.61
Plot of the real () and imaginary () parts of the ac susceptibility for V[DCPFS] measured at
100 Hz with 0 G dc bias.
ac susceptibility (arb. units)
9
8
7
6
5
4
3
2
1
0
0
50
100
T /K
150
200
250