Inorganic Chemistry
ARTICLE
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Rf = 0.6; H NMR (600 MHz, CDCl3, 25 °C, TMS) δ 9.99 (s, 1H,
compound: TLC (silica gel, CHCl3/MeOH 9:1) Rf = 0.8; MALDI-TOF
MS found m/z 1500.0 (MH+); HRMS (ESI) calcd for C117H39N4
CHO), 7.78 (d, J = 7.0 Hz, 2H, Ph-CHO), 7.60 (d, J = 7.3 Hz, 6H, Ph),
7.35 (d, J = 7.0 Hz, 2H, Ph-CHO), 6.91 (d, J = 7.3 Hz, 6H, Ph).
4-Formylphenyl-tris[4-{2-(4-pyridyl)ethynyl}phenyl]-
methane (sꢀTripod). In a Schlenk flask were placed 2 (116 mg, 1.6 ꢁ
10ꢀ4 mol), 4-ethynylpyridine (82 mg, 8.0 ꢁ 10ꢀ4 mol),15 Pd(PPh3)2Cl2
(13 mg, 1.9 ꢁ 10ꢀ5 mol), and CuI (3.7 mg, 1.9 ꢁ 10ꢀ5 mol) under Ar
atmosphere. Dry Et3N (0.5 mL) and dry THF (0.5 mL) were added to it,
and the mixture was degassedbyfreezeꢀthaw cycles. The reaction mixture
was stirred at room temperature under Ar atmosphere. After stirring for
1 h, further dry THF (1 mL) was added to the reaction mixture to
dissolve the insoluble solid. After stirring for 20 h, the reaction mixture
was diluted with chloroform, washed with water and dried over
anhydrous Na2SO4. The residue obtained by evaporation of the solvent
was purified with a silica gel column chromatography (CHCl3/MeOH
9:1). The fractions showing the signals of the target compound on
MALDI-TOF mass spectra were concentrated and reprecipitated with
hexane to remove a byproduct of 1,4-bis(4-pyridyl)butadiyne. Further
purification was performed with a silica gel column chromatography
(CHCl3/MeOH 9:1), giving 80.9 mg (78%) of the titled compound:
TLC (silica gel, CHCl3/MeOH 9:1) Rf = 0.3; MALDI-TOF MS found
m/z 652.6 (MH+); HRMS (FAB) calcd for C47H30N3O (MH+)
652.2389, found 652.2383; 1H NMR (600 MHz, CDCl3, 25 °C, TMS)
δ 10.02 (s, 1H, CHO), 8.60 (d, J = 6.0 Hz, 6H, Py), 7.83 (d, J = 8.2 Hz,
2H, Ph-CHO), 7.50 (d, J = 8.5 Hz, 6H, Ph), 7.43 (d, J = 8.2 Hz, 2H, Ph-
CHO), 7.37 (d, J = 6.0 Hz, 6H, Py), 7.25 (d. J = 8.5 Hz, 6H, Ph); 13C
NMR (150 MHz, CDCl3, 25 °C) δ 191.5, 152.0, 149.8, 146.1, 134.6,
131.6, 131.3, 131.1, 130.8, 129.3, 125.5, 120.6, 93.16, 87.31, 65.36.
C60ꢀsꢀTripod. In a Schlenk flask were placed sꢀTripod (15 mg,
2.3 ꢁ 10ꢀ5 mol), C60 (83 mg, 1.2 ꢁ 10ꢀ4 mol), and N-methylglycine
(107 mg, 1.2 ꢁ 10ꢀ3 mol). The flask was evacuated and replaced with Ar
gas. Toluene (10 mL) was added to it, and the mixture was heated at
100 °C and stirred for 21 h. The solvent was evaporated to give a crude
residue, which was passed through a short silica gel column by using
toluene, and then, CHCl3/MeOH 9:1 as eluents to remove excess C60.
The fractions eluted with CHCl3/MeOH 9:1 was collected and evapo-
rated. Further purification was performed with a silica gel column
chromatography (CHCl3/MeOH 99:1 to 98:2), giving 13 mg (41%)
of the titled compound: TLC (silica gel, CHCl3/MeOH 9:1) Rf = 0.6;
MALDI-TOF MS found m/z 1400.6 (MH+); HRMS (ESI) calcd for
C109H35N4 (MH+) 1399.2862, found 1399.2861; 1H NMR (600 MHz,
CDCl3, 25 °C, TMS) δ 8.60 (brs, 6H, Py), 7.52ꢀ7.77 (brs, 2H, Ph-
pyrrolidine), 7.41 (d, J = 8.2 Hz, 6H, Ph), 7.34 (brd, J = 4.8 Hz, 6H, Py),
7.25 (brs, Ph-pyrrolidine), 7.19 (d. J = 8.2 Hz, 6H, Ph), 4.98 (d, J = 9.6 Hz,
1H, pyrrolidine CH2), 4.96 (s, 1H, pyrrolidine CH), 4.28 (d, J = 9.6 Hz,
1H, pyrrolidine CH2), 2.90 (s, 3H, NꢀCH3); 13C NMR (150 MHz,
CDCl3, 25 °C) δ 156.19, 153.85, 153.29, 152.96, 149.76, 147.32, 147.28,
146.89, 146.65, 146.43, 146.27, 146.20, 146.11, 146.09, 145.95, 145.88,
145.72, 145.56, 145.52, 145.41, 145.36, 145.29, 145.21, 145.14, 144.98,
144.70, 144.68, 144.40 144.30, 143.16, 143.0,1 142.69, 142.58, 142.44,
142.21, 142.15, 142.07, 142.03, 141.92, 141.72, 141.67, 141.46, 140.21,
140.12, 139.71, 139.06, 136.50, 136.41, 135.97, 135.78, 135.72, 131.42,
131.26, 130.82, 128.79, 125.54, 120.20, 93.54, 87.18, 82.78, 77.37, 70.04,
68.93, 65.11, 40.05; UVꢀvis (CHCl3) 257 (5.17), 292 (5.08), 311
(5.06), 430 (3.56), 703.5 (2.60).
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1499.3175 (MH+), found 1499.3170; H NMR (600 MHz, CDCl3,
25 °C, TMS) δ 8.60 (d, J = 5.4 Hz, 6H, Py), 7.81 (brs, 2H, Ph-
pyrrolidine), 7.59 (d, J = 7.8 Hz, 2H, Ph-pyrrolidine), 7.47 (d, J = 9.0 Hz,
6H, Ph), 7.44 (d, J = 9.0 Hz, 2H, Ph0), 7.36 (d, J = 5.4 Hz, 6H, Py), 7.23
(d, J = 9.0 Hz, 6H, Ph), 7.18 (d, J = 9.0 Hz, 2H, Ph0), 4.99 (d, J = 9.6 Hz,
1H, pyrrolidine CH2), 4.95 (s, 1H, pyrrolidine CH), 4.27 (J = 9.6 Hz, 1H,
pyrrolidine CH2), 2.81 (s, 3H, NꢀCH3); 13C NMR (150 MHz, CDCl3,
25 °C) δ 156.1, 153.9, 153.1, 153.0, 149.8, 147.33, 147.31, 146.6, 146.4,
146.32, 146.30, 146.23, 146.20, 146.15, 146.01, 145.95, 145.7, 145.6,
145.52, 145.48, 145.42, 145.37, 145.29, 145.27, 145.24, 145.18, 144.7,
144.6, 144.42, 144.36, 143.2, 143.0, 142.7, 142.60, 142.56, 142.25,
142.24, 142.18, 142.14, 142.10, 142.05, 141.99, 141.9, 141.8, 141.7,
141.6, 140.21, 140.19, 139.9, 139.5, 140.22, 140.19, 139.9, 139.5, 137.6,
136.9, 136.4, 135.9, 135.7, 131.9, 131.5, 131.3, 131.2, 130.9, 130.8, 125.5,
123.1, 121.5, 120.4, 93.37, 89.83, 89.45, 87.19, 83.27, 70.00, 69.06, 65.03,
40.00; UVꢀvis (benzonitrile) 314 (5.02), 432 (3.42).
N-{4-(Triphenylmethyl)phenyl}-N0-(n-octyl)pyromellitdi-
imide (3). In a 20 mL flask were placed N-(n-octyl)pyromellitic
monoanhydride (100 mg, 3.0 ꢁ 10ꢀ4 mol),19 4-(triphenylmethyl)-
aniline (102 mg, 3.0 ꢁ 10ꢀ4 mol), and dry DMF (2 mL). The mixture
was purged with N2 gas and then heated at 130 °C for 6 h. A white
solid generated during cooling was collected by filtration and washed
with hexane, affording 117.6 mg (60%) of the titled compound. The
filtrate of the reaction mixture was evaporated and the residue was
recrystallized in acetic anhydride. The crystal was collected by
filtration and dried in vacuo, giving 26.7 mg (14%) of the titled
compound. Total yield was 144.3 mg (74%): TLC (silica gel, CHCl3)
Rf = 0.5; 1H NMR (600 MHz, CDCl3, 25 °C, TMS) δ 8.57 (s, 2H, Ph-
PI), 7.39 (d, J = 9.0 Hz, 2H, Ph0), 7.36 (d, J = 9.0 Hz, 2H, Ph0),
7.20ꢀ7.29 (m, 15H, Ph), 3.75 (t, J = 7.5 Hz, 2H, CαH2), 1.71
(quintet, J = 6.9 Hz, 2H, CβH2), 1.24ꢀ1.34 (m, 10H, CH2), 0.87 (t,
J = 6.9 Hz, 3H, CH3); 13C NMR (150 MHz, CDCl3, 25 °C) δ 166.2,
165.3, 147.3, 146.3, 137.6, 136.7, 131.9, 131.1, 128.8, 127.6, 126.1,
125.0, 118.7, 64.86, 38.82, 31.72, 29.10, 29.06, 28.41, 26.83,
22.58, 14.04.
N-[4-{Tris(4-bromophenyl)methyl}phenyl]-N0-(n-octyl)-
pyromellitdiimide (4). In a 20 mL flask were placed 3 (165 mg, 2.6 ꢁ
10ꢀ4 mol) and neat bromine (1 mL), and then the reaction mixture was
stirred for 30 min at room temperature. The reaction mixture was diluted
with CHCl3 (20 mL) and washed successively with an aqueous sodium
bisulfite solution and water. The organic layer was dried over anhydrous
Na2SO4, and the solvent was evaporated. The residue was purified with
silica gel column chromatography (CHCl3/hexane 1:2 to CHCl3/MeOH
9:1) to afford 201 mg (89%) of the titled compound: TLC (silica gel,
CHCl3) Rf = 0.8; 1H NMR (600 MHz, CDCl3, 25 °C, TMS) δ 8.37 (s,
2H, Ph-PI), 7.41 (d, J = 8.2 Hz, 8H, Ph and Ph0), 7.32 (d, J = 8.5 Hz, 2H,
Ph0), 7.08 (d, J = 8.2 Hz, 6H, Ph), 3.75 (t, J = 7.1 Hz, 2H, CαH2), 1.71
(brquintet, 2H, CβH2), 1.26ꢀ1.34 (m, 10H, CH2), 0.87 (t, J = 6.6 Hz,
3H, CH3); 13C NMR (150 MHz, CDCl3, 25 °C) δ 166.0, 165.1, 145.6,
144.4, 137.7, 136.6, 132.4, 131.4, 131.1, 129.4, 125.4, 120.8, 118.7, 63.80,
38.80, 31.69, 29.06, 29.02, 28.37, 26.78, 22.55, 14.02.
PIꢀTripod. Pd(PhCN)2Cl2 (2.6 mg, 6.8 ꢁ 10ꢀ6 mol), [(t-Bu)3-
PH]BF4 (3.9 mg, 1.4 ꢁ 10ꢀ5 mol), and CuI (1.3 mg, 6.8 ꢁ 10ꢀ6 mol)
were placed in a Schlenk flask and dissolved in dry dioxane (3 mL) and
dry (i-Pr)2NH (100 μL, 6.9 ꢁ 10ꢀ4 mol) under Ar atmosphere. The
solution was degassed by freezeꢀthaw cycles, and then 4 (120 mg, 1.4 ꢁ
10ꢀ4 mol) and 4-ethynylpyridine (70 mg, 6.8 ꢁ 10ꢀ4 mol)15 were added
to it. The reaction mixture was stirred for 11 h at room temperature. The
solvent was evaporated in vacuo, and the residue was extracted with
CHCl3 and washed with water. The solvent was evaporated, and the
residue was purified with flash silica gel column chromatography
(CHCl3/MeOH 95:5) to give a mixture including the target compound.
C60ꢀlꢀTripod. In a test tube with screw cap were placed lꢀTripod
(4.2 mg, 5.6 ꢁ 10ꢀ6 mol),11c C60 (20 mg, 2.8 ꢁ 10ꢀ5 mol), N-methyl-
glycine (25 mg, 2.8 ꢁ 10ꢀ4 mol), and toluene (1 mL), and the tube was
purged with N2 gas. The reaction mixture was heated to 100 °C and
stirred for 32 h. The resulting solution was passed through a short silica
gel column (toluene to CHCl3/MeOH 9:1) to remove excess C60. The
fraction eluted with CHCl3/MeOH 9:1 was collected and evaporated.
Further purification was performed with a silica gel column chromatog-
raphy (CHCl3/MeOH 99:1 to 98:2), giving 4.8 mg (57%) of the titled
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dx.doi.org/10.1021/ic201250q |Inorg. Chem. 2011, 50, 10249–10258