Crystal data for N-NN. C11H16N3O2, M ~ 222.27, mono-
clinic, space group P21/n (no. 14), a ~ 9.8453(16), b ~
the Ministry of Education, Culture, Sports, Science, and
Technology (MEXT), Japan.
3
˚
˚
16.530(3), c ~ 7.2587(9) A, b ~ 96.531(11)u, V ~ 1173.7(3) A ,
Z ~ 4, m(Mo-Ka) ~ 0.89 cm21, 2977 reflections measured,
2667 unique (Rint ~ 0.019) were used in all calculations. The
final R were 0.045 [Fo w 4s(Fo); 1788 data] and 0.078 (all data).
References and notes
1
T. Mallah, C. Hollis, S. Bott, M. Kurmoo, P. Day, M. Allan and
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910; B. Zhang, H. Tanaka, H. Fujiwara, H. Kobayashi,
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Crystal data for a-NN. C11H16N3O2, M ~ 222.27, mono-
clinic, space group P21/c (no. 14), a ~ 9.925(2), b ~ 9.317(2),
3
˚
˚
c ~ 12.972(3) A, b ~ 107.905(4)u, V ~ 1141.4(4) A , Z ~ 4,
m(Mo-Ka) ~ 0.9 cm21, 7487 reflections measured, 2584 unique
(Rint ~ 0.028) were used in all calculations. The final R were
0.048 [Fo w 4s(Fo); 1889 data] and 0.061 (all data).
Crystal data for b-NN. C11H16N3O2, M ~ 222.27, ortho-
rhombic, space group Pbca (no. 61), a ~ 13.0654(13), b ~
3
˚
˚
14.4171(19), c ~ 12.8740(17) A, V ~ 2425.0(5) A , Z ~ 8,
m(Mo-Ka) ~ 0.89 cm21, 3123 reflections measured, 2766
unique (Rint ~ 0.000) were used in all calculations. The final
R were 0.041 [Fo w 4s(Fo); 1992 data] and 0.067 (all data).
2
T. Sugawara, J. Synth. Org. Chem. Jpn., 1989, 47, 306–320;
K. Yamaguchi, H. Namimoto, T. Fueno, T. Nogami and
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Cryst., 1992, 218, 213–218.
Crystal data for N-PN. C17H20N3O2, M ~ 298.36, mono-
clinic, space group P21/a (no. 14), a ~ 12.284(4), b ~
3
3
4
T. Kimura, Y. Tomioka, H. Kuwahara, A. Asamitsu, M. Tamura
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˚
˚
12.657(5), c ~ 10.953(4) A, b ~ 111.72(2)u, V ~ 1582.2(10) A ,
Z ~ 4, m(Mo-Ka) ~ 0.84 cm21, 3933 reflections mea-
sured, 3579 unique (Rint ~ 0.059) were used in all calculations.
The final R were 0.059 [Fo w 4s(Fo); 1565 data] and 0.178
(all data).
T. Sugano, T. Fukasawa and M. Kinoshita, Synth. Metals, 1991,
41–43, 3281–3284; T. Sugimoto, S. Yamaga, M. Nakai, M. Tsuji,
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Commun., 1999, 2417–2418.
Magnetic measurements. The temperature dependence of
the magnetic susceptibility was measured using a Quantum
Design MPMS-5 SQUID magnetometer under a magnetic
field of 0.5 T. The diamagnetic component of the susceptibility
was estimated from plots of the high temperature data.
5
R. Kumai, M. M. Matsushita, A. Izuoka and T. Sugawara,
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Cyclic voltammetry. Cyclic voltammograms were recorded
at room temperature in benzonitrile solution in the presence
of 0.1 M tetra-n-butylammonium perchlorate (Nacalai Tesque
Inc.) as a supporting electrolyte with a platinum working
electrode, using a Hokuto Denko HAB 151 potentiostat/
galvanostat at room temperature. An Ag/AgCl electrode (BAS
Co.) was used as the reference electrode. The scanning rate
6
7
8
J. Nakazaki, Y. Ishikawa, A. Izuoka, T. Sugawara and
Y. Kawada, Chem. Phys. Lett., 2000, 319, 385–390.
J. Nakazaki, M. M. Matsushita, A. Izuoka and T. Sugawara, Mol.
Cryst. Liq. Cryst., 1997, 306, 81–88.
was 200 mV s21
.
J. A. Crayston, A. Iraqi and J. C. Walton, Chem. Soc. Rev., 1994,
147–153; H. Nishide, T. Kaneko, S. Toriu, Y. Kuzumaki and
E. Tsuchida, Bull. Chem. Soc. Jpn., 1996, 69, 499–508; H. Nishide,
T. Kaneko, T. Nii, K. Katoh, E. Tsuchida and P. M. Lahti,
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1997, 119, 1428–1438; H. Oka, T. Tamura, Y. Miura and Y. Teki,
J. Mater. Chem., 1999, 9, 1227–1232; T. Yamamoto and
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EPR measurement of oxidized species. EPR spectra of oxid-
ized species were measured on a JEOL JES-RE2X spectrometer
equipped with an Air Products LTR-3 liquid helium transfer
system. The temperature was controlled manually by adjusting
the helium gas flow rate. The temperature of the sample was
measured with an Advantest TR2114H digital multi-thermo-
meter with a gold–iron thermocouple. The microwave frequency
was recorded with an Advantest TR5212 counter, and the
resonance magnetic field value was measured with the aid of a
JEOL ES-FC5 NMR field meter. Zero-field parameters were
calculated using a high field approximation.
9
D. G. B. Boocock and E. F. Ullman, J. Am. Chem. Soc., 1968, 90,
6873–6874.
10 B. L. Bray, P. H. Mathies, R. Naef, D. R. Solas, T. T. Tidwell,
D. R. Artis and J. M. Muchowski, J. Org. Chem., 1990, 55, 6317–
6328.
11 E. F. Ullman, J. H. Osiecki, D. G. B. Boocock and R. Darcy,
J. Am. Chem. Soc., 1972, 94, 7049–7059.
Molecular orbital calculations. PM3/UHF molecular orbital
calculations were performed using the CAChe MOPAC
program provided by Sony Techtronics Inc. Without any
additional comment, a planar conformation is assumed.
12 J. K. Stille, Angew. Chem., Int. Ed. Engl., 1986, 25, 508–524.
13 In general, the lifetime of a radical cation of an a-vacant pyrrole
derivative is very short. For example, the lifetime of pyrrole and
N-(triisopropylsilyl)pyrrole radical cations were determined to
be 30 and 250 ms, respctively. The kinetic stability of the diradical
cations of pyrrolylNNs is considered to be very high compared
with these derivatives; see: C. P. Andrieux, P. Audebert, P. Hapiot
and J. M. Save´ant, J. Am. Chem. Soc., 1990, 112, 2439–2440;
C. P. Andrieux, P. Audebert, P. Hapiot and J. M. Save´ant, J. Phys.
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Acknowledgements
The authors thank Mr Onodera (JEOL) for carrying out high
resolution mass spectroscopy. This work was partly supported
by a Grant-in-Aid for Scientific Research (A) 13304056 from
J. Mater. Chem., 2003, 13, 1011–1022
1021