Self-Assembly of 3,6-Bis(4-triazolyl)pyridazine Ligands
1.091, Flack-parameter 0(10), largest difference peak and hole: 0.220/
(2,5,8,11,14,17,20,23,26,29,32,35-dodecaoxaheptatriacontan-37-yl)-1H-
1,2,3-triazol-4-yl)pyridazine (69 mg, 0.053 mmol) in CH2Cl2 (2 mL) was
added dropwise to a solution of tetrakis(acetonitrile)copper(I) hexafluor-
ophosphate (19 mg, 0.053 mmol) in CH2Cl2 (2 mL) and the solution was
stirred for 1 h at room temperature. After the addition of diethyl ether
(10 mL), the brown suspension was allowed to stand in the fridge over-
night. The diethyl ether was decanted and the pure product was obtained
after subsequent preparative size-exclusion chromatography (BioBeads
À0.229 eꢄÀ3
.
3,6-Bis(trimethylsilyl)ethynyl)pyridazine
(3):
Trimethylsilylacetylene
(2.85 mL, 20.2 mmol) was added through a syringe to a degassed solution
of 3,6-dibromopyridazine (2 g, 8.4 mmol), CuI (32 mg, 0.17 mmol), and
PdACHTUNGTRENNUNG(PPh3)4 (200 mg, 0.17 mmol) in THF/NEt3 (7:3, 60 mL), and the solu-
tion was stirred for 24 h at 258C. The salts formed were filtered off, and
the filtrate was evaporated under reduced pressure. The residue was puri-
fied by column chromatography on silica gel (chloroform as an eluent),
providing the product as an off-white powder (1.92 g, 84%). 1H NMR
(250 MHz, CDCl3, 258C): d=7.49 (s, 2H, CH), 0.29 ppm (s, 18H, CH3).
13C NMR (75 MHz, CDCl3, 258C): d=145.5, 128.9, 102.3, 100.4,
À0.5 ppm. Elemental analysis: calcd (%) for C14H20N2Si2: C 61.71, H
7.40, N 10.28; found: C 61.59, H 7.66, N 10.07.
1
SX-3, CH2Cl2) as a brown oil (58 mg, 73%). H NMR (250 MHz, CD2Cl2,
258C): d=8.79 (s, 8H, H-pyridazine), 8.38 (s, 8H, H-triazol), 4.66 (br,
16H, CH2), 4.01–3.35 (br, 392H, CH2 and CH3) ppm. 13C NMR (75 MHz,
CD2Cl2, 258C): d=71.6, 70.3, 69.0, 58.5 ppm. (aromatic carbon signals
are too low in intensity). MS (ESI): m/z (%): 1321.71 (100) [L+Na]+,
1865.83 (10) [4L+4Cu+PF6]3+, 2870.25 (10) [4L+4Cu+2PF6]2+. HRMS
(ESI) calcd for C232H424N32O96Cu4PF6 [MÀ3PF6]3+: 1865.5384; found:
3,6-Bis(1-(2,5,8,11,14,17,20,23,26,29,32,35-dodecaoxaheptatriacontan-37-
yl)-1H-1,2,3-triazol-4-yl)pyridazine (4): 3,6-Bis(trimethylsilyl)ethynyl)pyr-
idazine (50 mg, 0.2 mmol) was dissolved in a deaerated THF/water mix-
ture (5:1, 15 mL) and treated with a 3-fold excess of tris[(1-benzyl-1H-
1,2,3-triazol-4-yl)methyl]amine (TBTA; 200 mg, 0.6 mmol) under an
argon atmosphere. After 30 min the m-dPEG12 azide (250 mg,
0.43 mmol), CuSO4 (70 mg, 0.43 mmol), and sodium ascorbate (90 mg,
0.45 mmol, in 1 mL of water) was added and the suspension was stirred
for 72 h at 258C under an argon atomsphere. The solvent was evaporated
under vacuum and the residue was extracted by using chloroform/water
(containing an appropriate amount of EDTA). The organic phase was
dried over NaSO4, filtered, and the solvent was evaporated. Column
chromatography on silica acetone/methanol (1:1) and subsequent prepa-
rative size-exclusion chromatography (BioBeads SX-3, CH2Cl2) provided
the pure product as a brown oil (129 mg, 49%). 1H NMR (250 MHz,
1865.5397. HRMS (ESI) calcd for C232H424N32O96Cu4P2F12 [MÀ2PF6]2+
:
2870.7900; found: 2870.7826.
CCDC 787347 (2) contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cam-
request/cif
Acknowledgements
Financial support of this work by the Dutch Polymer Institute (DPI), the
Thꢀringer Kultusministerium (grant no. B715-08011) and the Fonds der
Chemischen Industrie is kindly acknowledged.
CD2Cl2, 258C): d=8.56 (s, 2H), 8.38 (s, 2H), 4.68 (t, 3J
N
3
4H), 3.98 (t, J
N
CH3). 13C NMR (75 MHz, CDCl3, 258C): d=71.8, 70.4, 69.2, 58.5 ppm
(aromatic carbon signals are too low in intensity). MS (ESI): m/z (%):
1299.74 (100) [M+H]+, 1321.72 (60) [M+Na]+. HRMS (ESI) calcd for
C58H107N8O24 [M+H]+: 1299.7393; found: 1299.7345.
[1] a) R. Hoogenboom, G. Kickelbick, U. S. Schubert, Eur. J. Org.
[2] a) M. Schmittel, V. Kalsani, D. Fenskeb, A. Wiegrefea, Chem.
Copper(I) complex of 3,6-bis(1-mesityl-1H-1,2,3-triazol-4-yl)pyridazine
(5):
3,6-Bis(1-mesityl-1H-1,2,3-triazol-4-yl)pyridazine
(25 mg,
0.055 mmol) in CH2Cl2 (2 mL) was added dropwise to a solution of tetra-
kis(acetonitrile)copper(I) hexafluorophosphate (21 mg, 0.055 mmol) in
CH2Cl2 (2 mL). The immediate red precipitate formed was filtered off
after 30 min and washed twice with CH2Cl2, yielding the pure product as
1
a red powder (35 mg, 98%). H NMR (250 MHz, [D6]acetone, 258C): d=
9.26 (s, 8H, H-pyridazine), 8.77 (s, 8H, H-triazol), 7.10 (s, 16H, H-mesi-
tyl), 2.35 (s, 24H, CH3), 1.92 ppm (s, 48H, CH3). 13C NMR (75 MHz,
[D6]acetone, 258C): d=151.5, 143.2, 142.3, 135.3, 133.1, 130.3, 130.1,
129.8, 21.1, 17.3 ppm. MS (ESI): m/z (%): 963.38 (70) [2L+Cu]+, 1623.51
[5] V. J. Catalano, M. A. Malwitz, S. J. Horner, J. Vasquez, Inorg. Chem.
(10)
[3L+2Cu+PF6]+.
Elemental
analysis:
calcd
(%)
for
C104H104Cu4F24N32P4: C 47.38, H 3.98, N 17.00; found: C 47.69, H 3.91, N
17.32.
Silver(I) complex of 3,6-bis(1-mesityl-1H-1,2,3-triazol-4-yl)pyridazine (6):
3,6-Bis(1-mesityl-1H-1,2,3-triazol-4-yl)pyridazine (25 mg, 0.055 mmol) in
CH2Cl2 (2 mL) was added dropwise to a solution of silver(I) hexafluor-
oantimonate (19 mg, 0.055 mmol) in CH2Cl2 (2 mL), and the solution was
stirred for 1 h at room temperature. After the addition of diethyl ether
(10 mL), the white precipitate was filtered off. The pure product was ob-
tained after recrystallization from dichloromethane/diethyl ether (1:1) as
a white powder (32 mg, 73%). 1H NMR (250 MHz, CD2Cl2, 258C): d=
8.61 (s, 8H, H-pyridazine), 8.34 (s, 8H, H-triazole), 7.08 (s, 16H, H-mesi-
tyl), 2.40 (s, 24H, CH3), 1.97 ppm (s, 48H, CH3). 13C NMR (75 MHz,
[D6]acetone, 258C): d=150.2, 142.5, 141.7, 134.7, 132.0, 129.4, 127.7,
[7] a) Z. Xu, L. K. Thompson in Comprehensive Coordination Chemis-
try II, Vol. 1 (Eds.: J. A. McCleverty, T. J. Meyer), Elsevier, Oxford,
2004, pp. 63–95; b) P. N. W. Baxter in Comprehensive Supramolec-
ular Chemistry, Vol. 9 (Eds.: J. L. Atwood, J. E. D. Davies, D. D.
Macnicol, F. Vçgtle), Pergamon, Oxford, 1996, pp. 165–211; c) F.
Thꢅbault, A. J. Blake, C. Wilson, N. R. Champness, M. Schrçder,
New J. Chem. 2006, 30, 1498–1508; d) E. C. Constable, C. E. House-
[8] a) M.-T. Youinou, N. Rahmouni, J. Fischer, J. A. Osborn, Angew.
733–735; b) B. L. Schottel, H. T. Chifotides, M. Shatruk, A. Chouai,
5895–5912; c) N.-D. Sung, K.-S. Yun, T.-Y. Kim, K.-Y. Choi, M. Suh,
380; d) N. Tsukada, T. Sato, H. Mori, S. Sugawara, C. Kabuto, S.
[9] E. C. Constable, C. E. Housecroft, M. Neuburger, S. Reymann, S.
127.2, 20.9, 16.9 ppm. MS (ESI): m/z (%):557.13 (100) [2L+2Ag]2+
,
1005.34 (40) [2L+Ag]+, 1349.13 (5) [2L+2Ag+SbF6]+, 1799.40 (4)
[3L+2Ag+SbF6]+. HRMS (ESI) calcd for C78H78Ag2N24SbF6
[MÀLÀ2AgÀ3SbF6]+: 1799.3880; found: 1799.3703. Elemental analysis:
calcd (%) for C104H104Ag4F24N32Sb4: C 39.32, H 3.30, N 14.11; found: C
39.29, H 3.31, N 14.01.
Copper(I) complex of 3,6-bis(1-(2,5,8,11,14,17,20,23,26,29,32,35-dodeca-
oxaheptatriacontan-37-yl)-1H-1,2,3-triazol-4-yl)pyridazine (7): 3,6-Bis(1-
Chem. Asian J. 2011, 6, 873 – 880
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
879