Determination of association constants K for complexes
j
(e): 330 (2565), 300 (11 116), 280 (25 000 M~1 cm~1) nm;
ass
max
1 Æ Mn‘9
2 : 1 complex j
(e): 330 (2006), 300 (12 510), 280 (24 643
max
M~1 cm~1) nm. 1a É CuNf 1 : 1 complex j
(e): 330 (5013),
2
max
To 2 ml of a 140 lM solution of a 1,10-phenanthroline
bridged calix[6]arene 1 in dry chloroform, a 2 mM solution of
the transition metal salt in dry acetonitrile was added in 9 ll
aliquots. In order to use non-nucleophilic anions, Co2`, Ni2`
and Cu2` ions were added as nonaÑuorobutanesulfonates
(Nf);7 Cu` was not available as the nonaÑuorobutane-
sulfonate and therefore was added as tetrakis(aceto-
nitrile)copper(I) hexaÑuorophosphate. The titration was
followed by UV, and from a shoulder at 330 nm the associ-
ation constants were calculated. In the case of Cu`, isosbestic
points were observed at 292 nm for 1a and at 295 nm for 1b.
300 (13 920), 280 (25 000 M~1 cm~1) nm; 2 : 1 complex j
max
(e): 330 (4411), 300 (11 818), 280 (23 571 M~1 cm~1) nm.
1a É [(CH CN) Cu]PF
j
(e): 330 (1571), 300 (9643), 292
3
4
6
max
(11 143), 280 (19 143 M~1 cm~1) nm. 1b É CoNf 1 : 1 complex
2
j
(e): 330 (1786), 305 (8857), 280 (19 429 M~1 cm~1) nm.
max
2 : 1 complex j
(e): 330 (1500), 305 (6929), 280 (19 286) nm.
max
1b É NiNf 1 : 1 complex j
(e): 330 (1571), 305 (8714), 280
2
max
(19 571 M~1 cm~1) nm. 2 : 1 complex j
(e): 330 (1357), 305
max
(7214), 280 (19 571 M~1 cm~1) nm. 1b É CuNf 1 : 1 complex
2
j
(e): 330 (2429), 305 (8286), 280 (18 643 M~1 cm~1) nm;
max
2 : 1 complex j
(e): 330 (2071), 305 (6357), 280 (18 286 M~1
max
cm~1) nm. 1b É [(CH CN) Cu]PF 1 : 1 complex j
(e): 330
Determination of the 1a Æ Cu‘ complex stoichiometry by the
method of continuous variations (““Job plotÏÏ)9
3
4
6
max
(2143), 305 (8286), 295 (13 571), 280 (18 143 M~1 cm~1) nm.
Mixtures of [(CH CN) Cu]PF and ligand 1a with ratios
1H-NMR spectra of 1 Æ CuPF complexes. 1a. 1H-NMR (200
3
4
6
6
varying from 10 : 0 to 0 : 10 but at a constant total concentra-
MHz, CDCl , D O exchange): d 8.25 (d, J \ 8.3, 2 H, 4-H,
3
2
tion ([M(CH CN) CuNPF ] ] [L]) were made from 1 mM
7-H), 7.82 (d, J \ 8.3, 2 H, 3-H, 8-H), 7.74 (s, 2 H, 5-H, 6-H),
6.97 (d, J \ 2.5, 4 H, ArÈH), 6.96 (s, 4 H, ArÈH), 6.88 (d,
3
4
6
solutions of 1a and M(CH CN) CuNPF in dry chloroformÈ
3
4
6
acetonitrile (1 : 1). The UV extinction at j \ 330 nm was
plotted against the molar fraction (see Fig. 1).
J \ 2.3, 4 H, ArÈH), 5.53 (s, 4 H, OCH ), 4.48 (d, J \ 15.3, 4
2
H, ArÈCH ÈAr), 3.84 (d, J \ 14.8, 2 H, ArÈCH ÈAr), 3.58 (d,
2
2
J \ 14.8, 2 H, ArÈCH ÈAr), 3.55 (d, J \ 15.4 Hz, 4 H,
ArÈCH ÈAr), 1.15 (s, 18 H, CH ), 1.10 (s, 36 H, CH ). Prior to
the D O exchange the OH signal appeared as a broad singlet
between ca. 7.3 and 8.0 ppm, overlapping the signals of the
2
General procedure for the synthesis of transition metal
complexes of 1a
2
3
3
2
To 50 lmol of 1a in 5È20 ml of dry dichloromethane, a solu-
tion of 50 lmol of a transition metal salt in 2 ml of dry meth-
anol was slowly added. After 2 h of stirring at room
temperature, the solvents were removed in vacuo. The residue
was recrystallized from benzeneÈdichloromethane or benzeneÈ
chloroform (see Table 1 for yields, melting points and elemen-
tal analyses).
1,10-phenanthroline bridge. 1a É CuPF 1H-NMR M300 MHz,
6
CDCl , ca. 1.3 equiv. of [(CH CN) Cu]PF N: d 8.58 (d,
3
3
4
6
J \ 8.2, 2 H, 4-H, 7-H), 7.99 (s, 2 H, 5-H, 6-H), 7.95 (d,
J \ 8.3, 2 H, 3-H, 8-H), 7.64 (br s, 4 H, OH), 6.96 (br s, 8 H,
ArÈH), 6.86 (s, 4 H, ArÈH), 5.60 (s, 4 H, OCH ), 4.50 (d,
2
J \ 15.0,
4
H, ArÈCH ÈAr), 3.82 (d, J \ 14.0,
2
H,
2
ArÈCH ÈAr), 3.58 (d, J \ 14.1, 2 H, ArÈCH ÈAr), 3.55 (d,
2
2
J \ 15.4 Hz, 4 H, ArÈCH ÈAr), 1.15 (s, 18 H, CH ), 1.10 (s, 36
IR (KBr) spectra of 1 Æ Mn‘ complexes. 1a É CoCl : l \ 3421
2
3
2
H, CH ). 1H-NMR M500 MHz, CD Cl ÈCD CN (10 : 1), ca.
(OH), 2959 (CH aliph.), 1654 (arom.), 1482, 1363, 1292, 1199,
3
2
2
3
1.5 equiv. of [(CH CN) Cu]PF , T \ 233 KN: d 8.73, 8.60,
1196, 1118, 873 (out-of-plane) cm~1. 1a É NiI : l \ 3422 (OH),
3
4
6
2
8.32 (br d, J B 10, br s, br s, 4 H), 8.15, 7.75 (s, br d, J B 10, 4
H), 7.48, 7.40, 7.32, 7.22 (br s, br s, br s, br d, J B 8, 7 H), 6.98,
6.91 (br s, br s, 4 H), 6.55, 6.50 (br s, br s, 2 H), 6.24, 6.14 (br s,
br s, 4 H), 4.25, 4.20 (br d, J B 15, br d, J B 15, 2 H), 4.05,
3.95, 3.80 (br d, J B 16, br d, J B 15, br d, J B 16, 6 H), 3.55,
3.47, 3.38 (br s, br d, J B 14, br d, J B 14, 3 H), 3.21, 2.95 (br
d, J B 14, br d, J B 14 Hz, 2 H), 1.25, 1.18 (br s, br s, 36 H),
2960 (CH aliph.), 1624 (arom.), 1482, 1362, 1292, 1198, 1119,
1029, 873 (out-of-plane) cm~1. 1a É CuBr : l \ 3385 (OH),
2
2960, 2867 (CH aliph.), 1654 (arom.), 1481, 1392, 1362, 1201,
1120, 981, 872 (out-of-plane) cm~1. 1a É CuBr: l \ 3414 (OH),
2959, 2867 (CH aliph.), 1654 (arom.), 1482, 1362, 1291, 1201,
981, 871, 818 (out-of-plane) cm~1. 1a É EuCl : l \ 3418 (OH),
3
2958 (CH aliph.), 1624 (arom.), 1482, 1363, 1292, 1200, 1119,
0.78, 0.66 (br s, br s, 18 H). 1b É CuPF 1H-NMR M300 MHz,
873 (out-of-plane) cm~1.
6
CDCl , ca. 1.3 equiv. [(CH CN) Cu]PF N: d 8.55 (d, J \ 8.2,
3
3
4
6
UV/Vis (CHCl ) spectra of 1 Æ Mn‘ complexes. 1a É CoNf
2 H, 4-H, 7-H), 8.46 (s, 2 H, 5-H, 6-H), 7.92 (d, J \ 8.2, 2 H,
3-H, 8-H), 7.20 (m, 6, H ArÈH), 6.99 (d, J \ 7.7, 4 H, ArÈH),
6.86 (d, J \ 7.7, 4 H, ArÈH), 6.65 (t, J \ 7.5, 4 H, ArÈH), 5.70
(s, 4 H, OCH ), 4.33 (br d, J \ 15.2, 4 H, ArÈCH ÈAr), 3.68
3
2
1 : 1 complex j
(e): 330 (2500), 300 (10 523), 280 (20 877
max
M~1 cm~1) nm; 2 : 1 complex j
(e): 330 (2387), 300
max
(12 444), 280 (21 714 M~1 cm~1) nm. 1a É NiNf 1 : 1 complex
2
2
2
(br d, J \ 15.1, 2 H, ArÈCH ÈAr), 3.50 (d, J \ 15.3, 4 H,
ArÈCH ÈAr), 3.41 (d, J \ 15.4 Hz, 2 H, ArÈCH ÈAr).
2
Table 1 Elemental analyses for 1a É MX
2
2
n
Formula
Elem. anal. calc. (%)
Elem. anal. found (%)
Notes and references
MX
Yield (%)
81
Mp/¡C
n
1
(a) C. D. Gutsche, Monographs in Supramolecular Chemistry, The
Royal Society of Chemistry, Cambridge UK, 1989, vol.
1
CuBr
CuBr
CoCl
[C
H
N O É CuBr] É CHCl
[250
80 92
2
6
3
(Calixarenes); (b) C. D. Gutsche, Monographs in Supramolecular
C 70.93, H 6.98, N 2.04
C 70.71, H 6.76, N 2.12
Chemistry, The Royal Society of Chemistry, Cambridge UK,
1998, vol.
6 (Calixarenes Revisited); (c) T opics in Inclusion
[C
H
N O É CuBr ]
72
65
75
86
[250
[250
245
2
80 92
2
6
2
Science, ed. J. Vincens and V. Bohmer, Kluwer Academic Publi-
shers, Dordrecht, Boston, London, 1991, vol. 3 (Calixarenes. A
Versatile Class of Macrocyclic Compounds); (d) V. Bohmer,
Angew. Chem., 1995, 107, 785; Angew. Chem., Int. Ed. Engl., 1995,
34, 713.
(a) C. Wieser, C. B. Dielman and D. Matt, Coord. Chem. Rev.,
1997, 165, 93; (b) A. Ikeda and S. Shinkai, Chem. Rev., 1997, 97,
1713; (c) A. T. Yordanov and D. M. Roundhill, Coord. Chem.
Rev., 1998, 170, 93; (d) R. Ludwig, FreseniusÏ J. Anal. Chem.,
2000, 367, 103.
D. Hesek, Y. Inoue, S. R. L. Everitt, M. Kuniede, H. Ishida and
M. G. B. Drew, T etrahedron: Asymmetry, 1998, 9, 4089.
C 68.59, H 6.62, N 2.00
C 68.40, H 6.62, N 1.90
[C
H
N O É CoCl ] É CH Cl
2
80 92
2
6
2
2 2
C 69.87, H 6.80, N 2.01
C 69.72, H 6.81, N 1.95
2
3
NiI
[(C
H
N O ) É NiI ]
2
80 92
2
6 2
2
C 72.03, H 6.95, N 2.10
C 72.11, H 7.10, N 1.94
EuCl
[C
H
N O É EuCl ] É C H
[250
3
80 92
2
6
3
6 6
C 68.22, H 6.52, N 1.85
C 68.11, H 6.79, N 1.85
New J. Chem., 2000, 24, 935È938
937