MCPs Derived from Linker-Directed Vertex Desymmetrization
A R T I C L E S
mL), and the solution was sparged with N2 gas for 30 min.
Pd(PPh3)4 (0.130 g, 0.112 mmol) was added, and the suspension
was stirred under N2 for 20 h at 100 °C in a pressure vessel. After
cooling, H2O (∼100 mL) was added, and a white solid precipitated.
The coupled product was collected by filtration and purified through
column chromatography on silica gel using CH2Cl2 as the eluent.
The material was hydrolyzed in a solution of KOH (1.5 M) in
dioxane/H2O (4:1, 20 mL) by heating at reflux for 18 h. The solvent
was evaporated, and the residue was dissolved in water. The solution
was acidified (pH ≈ 2) by addition of conc HCl. The resulting
white precipitate was collected by centrifugation, washed by
resuspending in water, and then recollected by centrifugation. After
multiple washing cycles the solid was dried under vacuum (0.92
g, 69%). Mp > 300 °C; 1H NMR (500 MHz, CDCl3): δ 13.14 (br,
3H), 8.29 (d, 2H, J ) 1.6 Hz), 8.26 (t, 1H, 1.6 Hz, 8.06 (m, 4H),
7.97, (m, 4H); 13C NMR (125 MHz, CDCl3): δ 167.1, 166.9, 143.1,
140.4, 132.5, 130.2, 130.0, 129.9, 127.3 HRMS (EI) (m/z) calcd
(found) for C21H14O6: 362.0790 (362.0805).
Hz), 8.08 (d, 2H, J ) 1.6 Hz), 8.04 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ (167.1, 166.5, 143.7, 140.8, 140.8, 140.3, 132.2, 131.9,
130.0, 129.9, 127.5, 125.6. HRMS (EI) (m/z) calcd (found) for
C28H18O8: 482.1002 (482.1007).
Preparation of H54. Dimethyl 5′-bromo-[1,1′:3′,1′′-terphenyl]-
4,4′′-dicarboxylate (1.00 g, 2.70 mmol), dimethyl isophthalate-5-
pinacolboronate (2.18 g, 6.49 mmol) and K3PO4 (3.45 g, 16.2 mmol)
were combined in 1,4-dioxane/H2O (9:1, 35 mL) and sparged with
N2 gas for 30 min. Pd(PPh3)4 (0.125 g, 0.108 mmol) was added,
and the suspension was stirred under N2 for 8 h at 100 °C in a
pressure vessel. After cooling the solvent was evaporated, and the
crude product was taken up in CH2Cl2. The solution was cooled
(-80 °C), and the precipitate was collected by cold filtration and
dried. The material was hydrolyzed in a solution of KOH (1 M) in
dioxane/H2O (2:1, 25 mL) by heating at reflux for 18 h. The solvent
was evaporated, and the residue was dissolved in water. The solution
was acidified (pH ≈ 2) through addition of conc M HCl. The
resulting white precipitate was collected by centrifugation, washed
by resuspending in water, and then recollected by centrifugation.
After multiple washing cycles the solid was dried under vacuum
Preparation of Intermediates for H43 and H54. 1,3,5-Tribro-
mobenzene (3.32 g, 10.5 mmol), methyl-4-carboxyphenylboronic
acid (4.17 g, 23.2 mmol,) and K3PO4 (13.4 g, 63.2 mmol) were
combined in 1,4-dioxane (125 mL) and sparged with N2 gas for 30
min. Pd(PPh3)4 (0.300 g, 0.260 mmol) was added, and the
suspension was stirred under N2 for 20 h at 100 °C in a pressure
vessel. After cooling, H2O (∼1 L) was added, and a white solid
precipitated. The precipitate was dissolved in CH2Cl2 and dried over
Na2SO4. The monocoupled and dicoupled esters were isolated using
column chromatography on silica gel with CH2Cl2 and hexanes
(75% CH2Cl2/25% hexanes to 100% CH2Cl2) as the eluent.
Dimethyl 5′-bromo-[1,1′:3′,1′′-terphenyl]-4,4′′-dicarboxylate: (3.12
1
(0.423 g, 31%). mp >300 °C H NMR (500 MHz, DMSO-d6): δ
13.15 (br, 5H), 8.54 (d, 4H, J ) 1.6 Hz), 8.49 (t, 2H, J ) 1.6 Hz),
8.04 (m, 7H), 13C NMR (125 MHz, DMSO-d6): δ 167.2, 167.0,
143.6, 140.9, 140.7, 140.2, 133.4, 131.3, 130.4, 129.9, 129.3, 127.4,
125.5, 125.3 HRMS (EI) (m/z) calcd (found) for C29H18O10 [M -
H]-: 525.0827 (525.0822).
Preparation of UMCM-151 [Cu2(C21H11O6)1.33]. Linker H22
(0.050 g, 0.14 mmol) was added to a solution of DMF/dioxane/
H2O (4:1:1, 10 mL) in a 20-mL scintillation vial. To this mixture
was added Cu(NO3)2 ·2.5H2O (0.096 g, 0.41 mmol), and the
contents were sonicated until dissolved and then heated at 85 °C.
After 12 h, the mother liquor was decanted and replaced with fresh
DMF/dioxane/H2O (4:1:1). The blue crystals were exchanged twice
in DMF and five times in acetone. The material was dried under
vacuum at room temperature for 4 h in which time the crystals
turned green. The yield of the reaction based upon the weight of
the solvent-free material is 80% based upon H32. Anal. Calcd
(Found) for [Cu2(C21H11O6)(H2O)5]: C, 52.39 (51.96) H, 2.89 (2.50).
Preparation of UMCM-152 [Cu2(C28H14O8)]. Linker H43
(0.050 g, 0.10 mmol) was added to a solution of 0.005 M HCl in
DMF/dioxane/H2O (4:1:1, 10 mL) in a 20-mL scintillation vial.
To this mixture, Cu(NO3)2 ·2.5H2O (0.096 g, 0.41 mmol) was added,
and the contents were sonicated until dissolved and then heated at
85 °C. After 12 h, the mother liquor was decanted and replaced
with fresh DMF/dioxane/H2O (4:1:1). Blue block-like crystals were
washed twice with DMF and five times with acetone. Solvent was
removed under vacuum for 4 h and further dried at 100 °C for
18 h to yield a dark-purple material. The yield of the reaction based
upon the weight of the solvent-free material is 82% based upon
H43. Anal. Calcd (Found) for [Cu2(C28H14O8)(H2O)1.5]: C, 53.17
(52.89) H, 2.71 (2.28).
Preparation of UMCM-153 [Cu2(C28H14O8)]. Linker H43
(0.050 g, 0.10 mmol) was added to a solution of NMP/dioxane/
H2O (4:1:1, 10 mL) in a 20-mL scintillation vial. To this mixture,
Cu(NO3)2 ·2.5H2O (0.096 g, 0.41 mmol) was added, and the
contents were sonicated until dissolved and then heated at 85 °C.
After 24 h, the mother liquor was decanted and replaced with fresh
NMP/dioxane/H2O (4:1:1). Blue blade-like crystals were washed
twice with DMF and five times with acetone. Solvent was removed
under vacuum for 4 h and further dried at 100 °C for 18 h to yield
a dark-purple material. The yield of the reaction based upon the
weight of the solvent-free material is 55% based upon H43. Anal.
Calcd (Found) for [Cu2(C28H14O8)(H2O)1.5]: C, 53.17 (53.37) H,
2.71 (2.50).
1
g, 31.6%) H NMR (500 MHz, CDCl3): δ 8.14 (m, 4H), 7.77 (d,
2H, J ) 1.6 Hz), 7.75 (t, 1H, J ) 1.6 Hz), 7.68 (m, 4H), 3.96 (s,
6H); 13C NMR (125 MHz, CDCl3): δ 166.7, 143.8, 142.7, 130.3,
129.8, 129.7, 127.2, 125.0, 123.6, 52.2. Methyl 3′,5′-dibromo-[1,1′-
biphenyl]-4-carboxylate: (1.61 g, 43.5%) 1H NMR (500 MHz,
CDCl3): δ 8.12 (m, 2H), 7.68 (s, 3H), 7.60 (m, 2H), 3.95 (s, 3H);
13C NMR (125 MHz, CDCl3): δ 166.7, 143.5, 142.6, 133.4, 130.3,
130.0, 129.2, 127.1, 123.4, 52.3.
Preparation of H43. Dimethyl 5′-bromo-[1,1′:3′,1′′-terphenyl]-
4,4′′-dicarboxylate (0.69 g, 1.6 mmol), dimethyl isophthalate-5-
pinacolboronate31 (0.63 g, 1.96 mmol) and K3PO4 (1.0 g, 4.8 mmol)
were combined in 1,4-dioxane/H2O (9:1, 15 mL) and sparged with
N2 gas for 30 min. Pd(PPh3)4 (0.037 g, 0.036 mmol) was added,
and the suspension was stirred under N2 for 16 h at 100 °C in a
pressure vessel. After cooling the solvent was evaporated, and the
crude product was taken up in CH2Cl2. The solution was cooled
(-80 °C), and the precipitate was collected by cold filtration and
dried. The material was hydrolyzed in a solution of KOH (1 M) in
dioxane/H2O (2:1, 20 mL) by heating at reflux for 18 h. The solvent
was evaporated, and the residue was dissolved in water. The solution
was acidified (pH ≈ 2) through addition of conc HCl. The resulting
white precipitate was collected by centrifugation, washed by
resuspending in water, and then recollected by centrifugation. After
multiple washing cycles the solid was dried under vacuum (0.54
1
g, 69%). H NMR (500 MHz, DMSO-d6): δ 13.24 (br, 4H), 8.56
(d, 2H, J ) 1.6 Hz), 8.52 (t, 1H, J ) 1.5 Hz), 8.10 (t, 1H, J ) 1.6
(25) Hong, S.; Oh, M.; Park, M.; Yoon, J. W.; Chang, J. S.; Lah, M. S.
Chem Commun. 2009, 5397–5399.
(26) Eddaoudi, M.; Nouar, F.; Eubank, J. F.; Wojtas, L.; Bousquet, T.;
Zaworotko, M. Supramolecular assemblies and building blocks. U.S.
Pat. Appl. 20090143596 A1, filed November 17th 2008.
(27) Weisstein, E. W. Platonic Solid. MathWorld: A Wolfram Web
(28) Wells, A. F.; The Third Dimension in Chemistry; Clarendon Press:
Oxford, London, 1956, p 143.
(29) Weisstein, E. W. Archimedean Solid. MathWorld: A Wolfram Web
(30) Percec, V.; Won, B. C.; Peterca, M.; Heiney, P. A. J. Am. Chem. Soc.
2007, 129, 11265–11278.
(31) Natera, J.; Otero, L.; Sereno, L.; Fungo, F.; Wang, N.-S.; Tsai, Y.-
M.; Hwu, T.-Y.; Wong, K.-T. Macromolecules 2007, 40, 4456–4463.
Preparation of UMCM-154 [Zn2(C29H14O10)]. Linker H54
(0.050 g, 0.095 mmol) was added to DMF (10 mL) in a 20-mL
scintillation vial. To this mixture, Zn(NO3)2 ·6H2O (0.14 g, 0.47
mmol) was added, and the contents were sonicated until dissolved
and heated at 85 °C. After 24 h the mother liquor was decanted
9
J. AM. CHEM. SOC. VOL. 132, NO. 39, 2010 13943