RT, approx. 200 ml aqueous NaCl was added and the aqueous
layer was extracted with DCM (3 ꢄ 150 ml). The organic layer
was washed with distilled water (3 ꢄ 150 cm3), dried with
sodium sulfate and the solvents were removed on an evapora-
tor. The crude product was purified by column chromatogra-
phy using petroleum ether (60–80 ꢀC)/ethyl acetate (9:1) to
give a white solid. (Yield 30%) 1H NMR, CDCl3 dH 0.84–
0.90 (6H, m), 1.12–1.67 (40H, m), 1.88 (1H, q), 4.14 (2H, d),
7.37–7.58 (4H, m), 7.69–7.81 (2H, m), 7.81–7.96 (2H, m),
8.05 (2H, s), m.p. 55–57 ꢀC. Found: C, 77.51; H, 8.99; N,
6.31. C43H59N3O3 requires C, 77.55; H, 8.99; N, 6.27%
and [H2L6]2þ were then optimised with the Gaussian98
program17 using the 6-31G* basis set.
Acknowledgements
We thank the EPSRC and the University of Reading for funds
for the Image Plate system. These studies were carried out
under the EU Nucelar Fission Safety Programme (Contract
FIKW-CT2000-0087).
L10. L10 was prepared according to the method described for
L2 using chelidamic acid and 2-aminothiophenol as starting
References
1
materials. (Yield 80%), H NMR DMSO-d6 dH 7.59 (4H, m),
7.81 (2H, s), 8.12 (2H, d), 8.23 (2H, d). Found: C, 57.43; H,
2.97; N, 10.59. C19H11N3S2O–2H2O requires C, 57.42; H,
3.80; N, 10.57%
1
2
3
4
J. N. Mathur, M. S. Murali and K. L. Nash, Ion Exch. Solvent
Extr., 2001, 357.
C. Madic, M. Lecomte, P. Baron and B. Bouillis, C.R.Physique,
2002, 3, 797.
L11. 1 g of L6 (2.8 mM) and 0.19 g of K2CO3 (1.45 mM)
were stirred at 120 ꢀC in DMF (20 ml) under nitrogen to 1-bro-
mododecane (0.67 ml, 2.8 mM) was added, the mixture was
cooled to 80 ꢀC and after 24 h, the solvent was removed under
vacuum. The black, crude material was crystallised from the
minimum amount of hot ethyl acetate to give L11 (Yield 1.1
g, 78%), 1H NMR, CDCl3 dH1.27 (s, 20H), 1.91 (q, 3H),
4.26 (t, 2H), 7.43 (m, 4H), 7.73 (d, 2H), 7.86 (d, 2H), 8.04 (s,
2H), m.p. 110–112 ꢀC.
P. Y. Cordier, C. Hill, P. Baron, C. Madic, M. J. Hudson and
J. O. Liljenzin, J. Alloys Compd., 1998, 271, 738.
˚
I. Hagstrom, L. Spjuth, A. Enarsson, J. O. Liljenzin, M. Ska¨lberg,
M. J. Hudson, P. B. Iveson, C. Madic, P. Y. Cordier, C. Hill and
N. Francois, Ion Exch. Solvent Extr., 1999, 17, 21.
M. G. B. Drew, P. B. Iveson, M. J. Hudson, J. O. Liljenzin,
L. Spjuth, P. Y. Cordier, A. Enarsson, C. Hill and C. Madic,
J. Chem. Soc., Dalton Trans., 2000, 821.
N. Boubals, M. G. B. Drew, C. Hill, M. J. Hudson, P. B. Iveson,
C. Madic, M. L. Russell and T. G. A. Youngs, J. Chem. Soc.,
Dalton Trans., 2002, 55.
Z. Kolarik, U. Mullich and F. Gassner, Ion Exch. Solvent Extr.,
1999, 17, 23.
Z. Kolarik, U. Mullich and F. Gassner, Ion Exch. Solvent Extr.,
1999, 17, 1155.
5
6
Metal complexes of L6. The La complex was prepared by
refluxing (27.5 mg, 0.064 mM) La(NO3)3ꢃ6H2O with 20 mg
(0.064 mM) ligand in 29 cm3 MeCN for 2 hours. The Nd com-
plex was prepared by refluxing 28 mg, 0.06 mM
Nd(NO3)3ꢃ6H2O with 20 mg (0.064 mM) ligand in 29 cm3
MeCN for 2 hours. The isomorphous Pr and Er complexes
were prepared similarly. The Gd complex was prepared by
refluxing 28.7 mg (0.064 mM) Gd(NO3)3ꢃ5H2O and 20 mg
(0.064 mM) ligand) in 32.5 cm3 MeCN for 2 hours. The iso-
morphous Eu compound was prepared similarly. All solutions
were left to cool slowly and crystals appeared after several
weeks.
7
8
9
C. Madic, M. J. Hudson, J. O. Liljenzin, J. P. Glatz, R. Nannicini,
A. Facchini, Z. Kolarik and R. Odoj, New Partitioning Techniques
for Minor Actinides, 2000, EUR 19149EN.
10 A. W. Addison and P. J. Burke, J. Heterocyclic Chem., 1981,
18, 803.
11 Comprehensive Heterocyclic Chemistry, ed. K. T. Potts, Pergamon
Press, 1984, vol. 5.
12 P. Froidevaux, J. M. Harrowfield and A. N. Sobolev, Inorg
Chem., 2000, 39, 4678.
13 M. J. Hudson, M. G. B. Drew, M. R. S. Foreman, C. Hill,
N. Huet, C. Madic and T. G. A. Youngs, Dalton Trans., 2003,
1673.
X-ray crystallography
The structures of six lanthanide complexes with L6 have been
determined. Crystal data and refinement details are provided
in Table 3. Data for all 6 crystals were collected with MoKa
radiation using the MARresearch Image Plate System. The
crystals were positioned at 70 mm from the Image Plate. 95
frames were measured at 2ꢀ intervals with a counting time of
2 min. Data analysis was carried out with the XDS program.20
Structure solution and refinement were carried out similarly.
Structures were solved using direct methods with the Shelx86
program.21 All non-hydrogen atoms were refined anisotropi-
cally, apart from the disordered water molecules in 1-La which
were refined isotropically. Hydrogen atoms on the carbon
atoms and nitrogen atoms were included in calculated posi-
tions and given thermal parameters equivalent to 1.2 times
those of the atom to which they were attached. Hydrogen
atoms on water molecules were not located. An empirical
absorption correction was made for the two metal complexes
using the DIFABS program.22 All structures were refined on
F2 till convergence using Shelxl.23 Crystallographic data have
been deposited at the Cambridge Crystallographic Data
Centre reference number CCDC 193084–193089. See http://
data in .cif or other electronic format.
14 M. G. B. Drew, M. J. Hudson, P. B. Iveson, C. Madic and M. L.
Russell, J. Chem. Soc., Dalton Trans., 2000, 2711; M. G. B. Drew,
M. J. Hudson, P. B. Iveson and C. Madic, Acta Cryst., 1998,
C56, 434.
15 M. G. B. Drew, M. J. Hudson, P. B. Iveson, C. Madic and M. L.
Russell, J. Chem. Soc., Dalton Trans., 1999, 2433.
16 S. Petoud, J.-C. G. Bunzli, K. J. Schenk and C. Piguet, Inorg.
Chem., 1997, 36, 1345.
17 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery,
Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam,
A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi,
V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C.
Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala,
Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K.
Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B.
Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.
Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham,
C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe,
P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong,
J. L. Andres, M. Head-Gordon, E. S. Replogle and J. A.
Pople, GAUSSIAN 98, Gaussian, Inc., Pittsburgh, PA,
1998.
18 G. Ionova, C. Rabbe, R. Guillauneux, S. Ionov, C. Madic, J. C.
Krupa and D. Guillaneus, New J. Chem., 2002, 26, 234.
19 Encyclopedia of Reagents for Organic Synthesis, ed.
L. A. Parquette, John Wiley and Sons, Chichester, U.K, 1995,
vol. 7.
20 W. Kabsch, J. Appl. Cryst., 1988, 21, 916.
Theoretical calculations
21 Shelx86 , G. M. Sheldrick, Acta Cryst., 1990, A46, 467.
22 N. Walker and D. Stuart, Acta Cryst., 1983, A39, 158.
23 G. M. Sheldrick, SHELXL, Program for refinement of crystal
structures, University of Go¨ttingen, Germany, 1993.
24 CERIUS2, Accelrys, San Diego, Calif. USA.
Starting models were built using the CERIUS2 software24 and
the three rings were made approximately coplanar but no
symmetry was imposed. All possible structures of L6, [HL6]þ
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
470
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 4 6 2 – 4 7 0