Soc., Chem. Commun., 1995, 995; (e) M. J. Cook and A. Jafari-Fini,
J. Mater. Chem., 1997, 7, 5; ( f ) D. M. Knawby and T. M. Swager,
Chem. Mater., 1997, 9, 535.
4 C. S. Velazquez, T. F. Baumann, M. M. Olmstead, H. Hope,
A. G. M. Barrett and B. M. Hoffman, J. Am. Chem. Soc., 1993, 115,
9997.
5 T. G. Linssen, K. Dürr, M. Hanack and A. Hirsch, J. Chem. Soc.,
Chem. Commun., 1995, 103.
6 R. D. George and A. W. Snow, Chem. Mater., 1994, 6, 1587.
7 (a) C. F. van Nostrum, S. J. Picken and R. J. M. Nolte, Angew.
Chem., Int. Ed. Engl., 1994, 33, 2173; (b) C. F. van Nostrum and
R. J. M. Nolte, Chem. Commun., 1996, 2385; (c) C. F. van Nostrum,
Adv. Mater., 1996, 8, 1027.
29.68, 28.29, 28.17, 22.54, 22.43, 13.98, 13.90; λmax/nm (toluene)
(ε) 324.5 (133 580), 636.0 (45 037), 664.5 (42 654), 700.0
(33 459).
2,14,26,38-Tetrakis[4,5-bis(hexylthio)-1,3-dithiol-2-ylidene]-
4H,6H,10H,12H,16H,18H,22H,24H,28H,30H,34H,36H,
40H,42H,46H,48H-tetrakis([1,3]dithiolo[4,5-c]dioxecino)[7,8-
b;7Ј,8Ј-k;7Љ,8Љ-t;7ٞ,8ٞ-cЈ]phthalocyanine 14
Following the procedure for the preparation of 2, compound 14
was synthesised from compound 9 (31 mg) and lithium pentox-
ide [from lithium (55 mg) and dry pentanol (5 ml)] and isolated
as a dark green amorphous solid (yield 15 mg, 48%) (Calc. for
C120H146N8O8S24: C, 55.48; H, 5.67; N, 4.31. Found: C, 55.39; H,
5.77; N, 4.48%); MALDI-MS, m/z, Found 2588; Calc. for
C120H146N8O8S24 2594; δH (CDCl3) ca. 8.2 (v br), ca. 4.6 (br), ca.
4.1 (br), 2.82 (br), 1.33 and 0.93 (overlapping br peaks); λmax/nm
(toluene) (ε) 333.0 (85 493), 648.5 (39 303), 674.5 (49 320), 709.0
(43 894) nm.
8 J. Vacus and J. Simon, Adv. Mater., 1995, 7, 797.
9 (a) M. J. Cook, G. Cooke and A. Jafari-Fini, J. Chem. Soc., Chem.
Commun., 1995, 1715; (b) M. J. Cook, G. Cooke and A. Jafari-Fini,
Chem. Commun., 1996, 1925.
10 M. A. Blower, M. R. Bryce and W. Devonport, Adv. Mater., 1996, 8,
63.
11 (a) F. Wudl, D. Wobschall and E. J. Hufnagel, J. Am. Chem. Soc.,
1972, 94, 671; (b) K. Deuchert and S. Hünig, Angew. Chem., Int. Ed.
Engl., 1978, 17, 875.
12 For reviews of TTF synthesis see: (a) M. Narita and C. V. Pittman,
Synthesis, 1976, 489; (b) A. Krief, Tetrahedron, 1986, 42, 1237;
(c) G. Schukat and E. Fanghänel, Sulfur Reports, 1993, 13, 254.
13 For related reactions with TTF derivatives see: (a) P. Blanchard,
M. Sallé, G. Duguay, M. Jubault and A. Gorgues, Tetrahedron Lett.,
1992, 33, 2685; (b) R. P. Parg, J. D. Kilburn, M. C. Petty, C. Pearson
and T. G. Ryan, J. Mater. Chem., 1995, 5, 1609.
14 (a) P. A. Barrett, D. A. Frye and R. P. Linstead, J. Chem. Soc., 1938,
1157; (b) review: C. C. Leznoff in ref. 1(a), 1989, vol. 1, p. 1.
15 D. M. Terekhov, K. J. M. Nolan, C. R. McArthur and C. C.
Lenznoff, J. Org. Chem., 1996, 61, 3034.
X-Ray crystallography
The X-ray diffraction experiment on 11 was carried out at T
150 K on a Siemens 3-circle diffractometer with a CCD area
detector, using graphite-monochromated Mo-Kα radiation,
-
λ = 0.710 73 Å. Crystal data: C20H32O2S6, M = 496.8; mono-
clinic, space group P21/c (No. 14), a = 25.359(2), b = 12.554(1),
c = 7.867(1) Å, β = 97.26(1)Њ, V = 2484.4(4) Å3 (from 442 setting
reflections with 10 < θ < 23Њ), Z = 4, Dc = 1.33
g ,
cmϪ3
F(000) = 1056, µ = 5.7 cmϪ1, crystal size 0.5 × 0.25 × 0.06 mm.
12 298 data with 2θ р 48Њ were collected in ω scan mode (0.3Њ
steps); of these 3874 data were unique and 2120 ‘observed’ with
I у 2σ(I). Semi-empirical absorption correction on Laue
equivalents was performed, min/max transmission 0.69/0.98,
Rint = 0.16 before and 0.14 after correction. The structure was
solved by direct methods and refined by full-matrix least
squares against F 2 of 3091 non-negative data, sing SHELXTL
software.25 Ordered non-H atoms were refined anisotropically,
disordered C atoms isotropically [C(8) to C(12) with 50%
occupancies, C(14) to C(18) with 33%] with C᎐C bonds
restrained to 1.53(1) Å. Hydroxy H atoms refined, other H
atoms ‘riding’ (265 variables, 25 restraints), converging at wR
(F 2, all data) = 0.292, goodness-of-fit 1.17, R(F, obs. data) =
16 A. Beeby and C. F. Stanley, unpublished data.
17 Review: A. B. P. Lever, E. R. Milaeva and G. Speier in ref. 1(a),
vol. 3, p. 1.
18 (a) D. C. Green, J. Org. Chem., 1979, 44, 1476; (b) A. S. Batsanov,
M. R. Bryce, J. N. Heaton, A. J. Moore, P. J. Skabara, J. A. K.
Howard, E. Ortí, P. M. Viruela and R. Vireula, J. Mater. Chem.,
1995, 5, 1689; (c) D. L. Lichtenberger, R. L. Johnston, K. Hinkel-
mann, T. Suzuki and F. Wudl, J. Am. Chem. Soc., 1990, 112, 3302,
and references therein; (d) A. J. Moore and M. R. Bryce, J. Chem.
Soc., Chem. Commun., 1991, 1638.
19 (a) Review: M. Adam, K. Müllen, Adv. Mater., 1994, 6, 439; (b) M.
Jørgensen, K. A. Lerstrup and K. Bechgaard, J. Org. Chem., 1991,
56, 5684; (c) M. R. Bryce, G. J. Marshallsay and A. J. Moore,
J. Org. Chem., 1992, 57, 4859; A. Dolbecq, K. Boubekeur, P. Batail,
E. Canadell, P. Auban-Senzier, C. Coulon, K. Lerstrup and
K. Bechgaard, J. Mater. Chem., 1995, 5, 1707.
0.099; residual electron density features ∆ρmax = 0.39, ∆ρmin
=
Ϫ0.51 e ÅϪ3. Atomic coordinates and displacement parameters,
bond distances and angles have been deposited at the
Cambridge Crystallographic Data Centre.†
20 (a) M. R. Bryce, G. Cooke, A. S. Dhindsa, D. J. Ando and
M. B. Hursthouse, Tetrahedron Lett., 1992, 33, 1783; (b)
M. Fourmigué and Y.-S. Huang, Organometallics, 1993, 12, 797.
21 J. Y. Becker, J. Bernstein, A. Ellern, H. Gershtenman and
V. Khodorkovsky, J. Mater. Chem., 1995, 5, 1557.
22 C. S. Wang, M. R. Bryce, A. S. Batsanov and J. A. K. Howard,
Chem. Eur. J., in the press.
Acknowledgements
23 We note that molecular dynamics simulations of the interactions of
segments of poly(γ-benzyl glutamate) in solution suggest that the
preferred conformation of macromolecules can be very solvent
dependent: J. Helfrich, R. Hentschke, Macromolecules, 1995, 28,
3831.
24 For a review of hydrogen bonding in functionalised TTF derivatives:
M. R. Bryce, J. Mater. Chem., 1995, 5, 1481.
25 G. M. Sheldrick, SHELXTL, Version 5/VMS, Siemens Analytical
X-Ray Instruments Inc., Madison, WI, USA, 1995.
We thank EPSRC for funding this work.
† For details of the CCDC deposition scheme, see ‘Instructions for
Authors’, J. Chem. Soc., Perkin Trans. 2, 1997, Issue 1. Any request to
the CCDC for this material should quote the full literature citation and
the reference number 188/84.
26 A. T. Rhys-Williams, S. A. Winfield and J. N. Miller, Analyst, 1983,
108, 1067.
27 Z. Xianfu, M. Jinshi and X. Huijan, SPIE J, 1991, 1616, 372.
28 M. S. C. Foley, PhD Thesis, Imperial College, London, 1994.
29 P. Wu, G. Saito, K. Imaeda, Z. Shi, T. Mori, T. Enoki and
H. Inokuchi, Chem. Lett., 1986, 441.
30 G. E. F. Gracey and W. R. Jackson, J. Chem. Soc. B, 1969, 1207.
31 A. Fischer, G. N. Henderson, L. M. Iyer and C. J. Chag, Can. J.
Chem., 1985, 63, 2390.
References
1 Reviews: (a) Phthalocyanines, Properties and Applications, ed.
C. C. Leznoff and A. B. P. Lever, vols. 1–3, VCH, New York, 1989–
1993; (b) H. Schultz, H. Lehmann, M. Rein and M. Hanack, Struct.
Bonding (Berlin), 1990, 74, 41; (c) M. Hanack and M. Lang, Adv.
Mater., 1994, 6, 819; (d) M. J. Cook, J. Mater. Chem., 1996, 6, 677.
2 D. Lelievre, O. Damette and J. Simon, J. Chem. Soc., Chem. Com-
mun., 1993, 939.
3 (a) F. Fernandez-Lazaro, A. Sastre and T. Torres, J. Chem. Soc.,
Chem. Commun., 1994, 1525; (b) N. Kobayashi, Y. Higashi and
T. Osa, J. Chem. Soc., Chem. Commun., 1994, 1785; (c) P. J. Brach,
S. J. Grammatica, O. A. Ossanna and L. Weinberger, J. Heterocycl.
Chem., 1970, 7, 1403; (d) B. Mohr, G. Wegner and K. Ohta, J. Chem.
Paper 7/01703K
Received 11th March 1997
Accepted 15th May 1997
1678
J. Chem. Soc., Perkin Trans. 2, 1997