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The starting material dissolved initially, before phthalhydrazide pre-
cipitated. Following heating at reflux, the suspension was then
cooled to room temperature and filtered. The filtrate was taken to
dryness, yielding a white solid, and the solid was dried thoroughly
under high vacuum. The solid was washed with cold water (1ꢁ
5 mL) and dried under high vacuum to yield apdpt as a white
Preparation of 2,5,8,11,14-pentaoxaheptadecan-17-oic acid NHS:
2,5,8,11,14-Pentaoxaheptadecan-17-oic acid (0.67 g, 2.3 mmol) and
DCC (0.49 g, 2.3 mmol) were dissolved in anhydrous CH2Cl2 (25 mL)
before NHS (0.27 g, 2.3 mmol) was added. The resulting suspension
was stirred for 18 h at room temperature before being filtered. The
filtrate was reduced in volume to 10 mL and cooled at 48C for 4 h,
which resulted in precipitation of a further crop of white solid. The
suspension was filtered and the filtrate taken to dryness to yield
2,5,8,11,14-pentaoxaheptadecan-17-oic acid NHS ester (0.913 g, ca.
100%) as a colourless oil that was used without further purifica-
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powder (0.249 g, 69%). H NMR ([D6]DMSO): d=8.40 (d, J=4.6 Hz,
2H; H1), 7.89–7.92 (m, 4H; H4 and H2), 7.37–7.41 (m, 2H; H3), 7.25
(d, J=8.3 Hz, 2H; H5), 7.18 (d, J=8.3 Hz, 2H; H6), 3.70 ppm (s, 2H;
H7); elemental analysis calcd (%) for C16H16N6: C 69.50, H 4.91,
25.59; found: C 69.34, H 4.97, N 25.59.
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tion. H NMR (CDCl3): d=3.83 (t, J=6.5 Hz, 2H; -C(=O)CH2CH2O-),
3.69–3.50 (m, 16H; CH2), 3.36 (s, 3H; OCH3), 2.88 (t, J=6.5 Hz, 2H;
-C(=O)CH2CH2O-), 2.81 ppm (brs, 4H; NHS-CH2).
Preparation of prdpt: The reactive amino-containing ligand apdpt
(0.142 g, 0.43 mmol) and pyrene carboxylic acid NHS ester were
dissolved in dry DMF (10 mL) and the solution heated to 808C for
18 h. The solution was cooled to room temperature, which resulted
in precipitation of a white solid. The solid was filtered, washed
with cold DMF (2ꢁ5 mL) and CH2Cl2 (2ꢁ5 mL), then dried in air to
Preparation of pgdpt: The reactive amino-containing ligand
apdpt (0.3 g, 0.91 mmol) and 2,5,8,11,14-pentaoxaheptadecan-17-
oic acid NHS ester (0.35 g, 0.91 mmol) were dissolved in anhydrous
DMF (10 mL) and the solution was heated to 808C for 18 h. After-
wards, all solvent was removed in vacuo and the residue was dried
under high vacuum to remove residual traces of DMF. The residue
was then dissolved in CH2Cl2 (40 mL) and the organic layer was
washed with a saturated aqueous solution of Na2CO3 (10 mL). The
organic phase was separated, dried with MgSO4, filtered, taken to
dryness and the residue was purified by column chromatography
on silica gel, eluting with 9:1 CH2Cl2/MeOH (Rf =0.55), to yield
pgdpt as a colourless oil (0.31 g, 56%). 1H NMR (CDCl3): d=8.35
(ddd, J=5.0, 1.8, 0.9 Hz, 2H; H1), 8.00 (dt, J=7.9, 1.0, 1.0 Hz, 2H;
H4), 7.73 (td, J=7.8, 7.8, 1.7 Hz, 2H; H2), 7.23–7.14 (m, 6H; H3 +
H5 +H6) 7.10 (t, J=6.4 Hz, 1H; NH), 4.48 (d, J=6.0 Hz, 2H; H7), 3.76
(t, J=5.7 Hz, 2H; H8), 3.66–3.42 (m, 16H; CH2), 3.31 (s, 3H; OCH3)
2.52 ppm (t, J=5.6 Hz, 2H; H9); elemental analysis calcd (%) for
C31H38N6O6·0.9H2O: C 61.35, H 6.61, N 13.85; found: C 61.54, H
6.67, N 14.00; weight loss upon heating calcd (%) for loss of
0.9H2O from C31H38N6O6·0.9H2O: 2.7; found: 3.1.
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yield prdpt as a white powder (0.144 g, 60%). H NMR ([D6]DMSO):
d=9.28 (t, J=6.1 Hz, 1H; NH), 8.46 (d, J=9.3 Hz, 1H; pyrene-H),
8.42 (d, J=4.4 Hz, 2H; H1), 8.36 (m, 2H; pyrene-H), 8.17–8.30 (m,
5H; 3ꢁpyrene-H+H4), 8.13 (t, J=7.6 Hz, 1H; pyrene-H), 7.98 (m,
2H; pyrene-H), 7.94 (td, J=7.7, 7.7, 1.7 Hz, 2H; H3), 7.39–7.45 (m,
4H; H2 +H5), 7.32 (d, J=8.3 Hz, 2H; H6), 4.65 ppm (d, J=6.1 Hz,
2H; H7); elemental analysis calcd (%) for C36H24N6O: C 77.68, H 4.35,
N 15.10; found: C 77.38, H 4.36, N 15.40.
Preparation of 1-pyrene butyric acid NHS ester: 1-Pyrene butyric
acid (0.2 g, 0.69 mmol) was suspended in anhydrous CH2Cl2
(20 mL) before N,N’-dicyclohexylcarbodiimide (DCC; 0.142 g,
0.69 mmol) and NHS (0.08 g, 0.69 mmol) were added. The reaction
was stirred at room temperature for 18 h, during which time a
white solid precipitated. The suspension was filtered and the fil-
trate taken to dryness. The residue was purified by column chro-
matography on silica gel, eluting with 1:1 petroleum ether (40–
608C boiling point range)/ethyl acetate (Rf =0.7), to yield 1-pyrene
Preparation of tpdpt: The reactive amino-containing ligand apdpt
(0.2 g, 0.61 mmol) and thioctic acid NHS ester (0.2 g, 0.66 mmol)
were dissolved in dry DMF (10 mL) and the solution was heated to
808C overnight. All solvent was removed in vacuo to yield an off-
white solid. The solid was dried under high vacuum for several
hours to remove residual DMF before being dissolved in CH2Cl2
(30 mL), and the organic phase washed with a saturated aqueous
solution of Na2CO3 (30 mL). The organic phase was separated,
dried with MgSO4, filtered and taken to dryness to yield an off-
white solid. The solid was further purified by column chromatogra-
phy on silica gel (9:1 CH2Cl2/MeOH, Rf =0.5) to yield tpdpt as a
beige powder (0.198 g, 63%). 1H NMR (CDCl3): d=8.34 (d, J=
5.0 Hz, 2H; H1), 8.00 (d, J=8.0 Hz, 2H; H4), 7.73 (t, J=7.8 Hz, 2H;
H2), 7.13–7.25 (m, 6H; H3, H5 and H6), 6.13 (brs, 1H; NH), 4.48 (d,
J=6.0 Hz, 2H; H7), 1.40–3.62 ppm (m, 13H; CH2 and CH); elemental
analysis calcd (%) for C27H28N6S2O: C 62.77, H 5.46, N 16.27, S 12.41;
found: C 62.93, H 5.55, N 16.18, S 12.15.
1
butyric acid NHS ester as a beige powder (0.206 g, 87%). H NMR
(CDCl3): d=9.24 (t, J=6.1 Hz, 1H; NH), 8.28 (d, J=9.3 Hz, 1H;
pyrene), 8.09–8.17 (m, 6H; pyrene), 8.02 (s, 2H; pyrene), 7.98 (t, J=
7.7 Hz, 1H; pyrene), 7.87 (d, J=7.8 Hz, 1H; pyrene), 3.47 (dd, J=
7.0, 8.5 Hz, 2H; C(=O)CH2), 2.86 (s, 2H; NHS-CH2), 2.72 (t, J=
7.1 Hz, 2H; -CH2-pyrene), 2.30 ppm (quin, J=7.4 Hz, 2H; CH2-CH2-
CH2); elemental analysis calcd (%) for C21H13NO4: C 74.40, H 5.46, N
4.08; found: C 74.53, H 5.61, N 3.71.
Preparation of pbdpt: The reactive amino-containing ligand
apdpt (0.1 g, 0.3 mmol) and 1-pyrene butanoic NHS ester (0.118 g,
0.3 mmol) were dissolved in dry DMF (10 mL) and the solution
heated to 808C overnight. Afterwards, all solvent was removed in
vacuo and the resulting white solid was dried further under
vacuum to remove all traces of DMF. The dried solid was dissolved
in CH2Cl2 (40 mL) and the organic phase was washed with a satu-
rated aqueous solution of Na2CO3 (40 mL). The organic phase was
separated, dried with MgSO4, filtered, taken to dryness and the res-
idue was purified by column chromatography on silica gel, eluting
with 9:1 CH2Cl2/MeOH (Rf =0.25), to yield pbdpt as a beige
powder (0.166 g, 36%) after drying under high vacuum. 1H NMR
(CDCl3): d=8.26 (m, 3H; H1 +1ꢁpyrene-H), 8.14 (d, J=7.6 Hz, 2H;
pyrene-H), 8.07 (m, 2H; pyrene-H), 7.99 (m, 5H; H4 +3ꢁpyrene-H),
7.82 (d, J=7.8 Hz, 1H; pyrene-H), 7.67 (td, J=7.8, 7.8, 1.8 Hz, 2H;
H3), 7.18 (m, 4H; H5 +H6), 7.11 (ddd, J=7.7, 4.8, 1.2 Hz, 2H; H2),
5.71 (brs, 1H; NH), 4.47 (d, J=6.0 Hz, 2H; H7), 3.39 (t, J=7.4 Hz,
2H; H8), 2.32 (t, J=7.2 Hz, 2H; H10), 2.24 ppm (m, 2H; H9); elemen-
tal analysis calcd (%) for C39H30N6O: C 78.24, H 5.05, N 14.04;
found: C 77.97, H 5.25, N 13.62.
Inorganic synthesis
Preparation of 1:
A
solution of [FeII(py)4(NCBH3)2] (0.011 g,
0.025 mmol) in CHCl3/MeOH (1:1, 2 mL) was added to a solution of
tpdpt (0.025 g, 0.05 mmol) in CHCl3/MeOH (1:1, 4 mL), resulting in
a dark-red solution. The solution was stirred for 1 h before diethyl
ether vapour was diffused in to yield a dark reddish-brown solid.
The solid was filtered and dissolved in CH2Cl2/MeOH (1:1, 4 mL)
before diethyl ether vapour was diffused into the solution. The re-
sulting red solid was filtered and dried under high vacuum for 4 h
to yield 1 (0.019 g, 63%). ESI-MS (+): m/z: 517.18 [M+H]+; elemen-
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ChemPlusChem 2018, 83, 1 – 9
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