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Electronic Supporting Information (ESI)
Void and filled supramolecular nanoprisms - Notable differences
between seemingly identical construction principles
Michael Schmittel,* Bice He
Center for Micro- and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein-Strasse, D-57068 Siegen, Germany,
1.1 General
All reagents were commercially available and used without further purification. Purifi-
cation and drying of the used solvents was performed according to standard methods.
Thin-layer chromatography was performed using thin-layer chromatography plates
(Silica Gel 60 F254, Merck). Silica Gel 60 was used for column chromatography.
Confirmation of the structures of all products was obtained by 1H-NMR and 13C-NMR
spectroscopy (Bruker AC200 and Avance AC 400 spectrometer, using the deuterated
solvent as the lock and residual solvent as the internal reference). The numbering of the
carbon atoms of the molecular formulae shown in the experimental section is used only
for the NMR assignments and is not in accordance with the IUPAC nomenclature rules.
Melting points were taken using a melting point apparatus of Dr. Tottoli (Büchi) and are
uncorrected. Electrospray mass spectra (ESI-MS) were recorded using a ThermoQuest
LCQ Deca. The purity of all compounds was checked by thin-layer chromatography on
SiO2 (silica gel 60 F254, Merck). Infrared spectra were recorded on a Perkin Elmer 1750
FT-IR spectrometer with the software of IRDM 1700. UV/Vis spectra were recorded on a
J&M Tidas II/Rev. 1 UV/visible Spectrometer. The degree of lithiation can readily be
monitored by GC, while the progress of substitution at phenanthroline is best controlled
by ESI-MS.
1. Experimental Section
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
2
1.2 Synthesis
1.2.1 Synthesis of trisphenanthroline TP
NN
OH
N
N
HO
N
N
OH14
567
8
9 10
1112
13
14
TP
3-Ethynyl-2-(4-hydroxy-2,6-dimethylphenyl)-9-mesityl-[1,10]-phenanthroline 1 (500 mg,
1.13 mmol), 1,3,5-triiodobenzene (171 mg, 376 μmol) and Pd[(PPh3)4] (69.0 mg,
60.0 μmol) were dissolved in dry DMF (30 mL) and dry triethylamine (30 mL). After
deoxygenating the reaction mixture with nitrogen gas for 15 min., it was heated to 60 °C
for 4 hours. Then water (200 mL) was slowly added and the resulting precipitate was
collected by filtration. After the collected solid had been washed with 100 mL of water,
30 mL of acetone and 100 mL of dichloromethane, the crude product was purified by
recrystallisation from DMF to obtain product as yellow solid (480 mg, 343 μmol, 91%).
MP: >300 °C; IR (KBr): ν~ = 3432 (w), 3413 (w), 2918 (w), 2358 (w), 1656 (s), 1615 (s),
1588 (s), 1542 (w), 1508 (w), 1459 (s), 1390 (m), 1317 (s), 1158 (s), 1030 (w), 889 (m),
850 (s), 776 (w), 639 (w); 1H-NMR (DMF-d7, 400 MHz): δ = 2.03 (s, 18H, 10-H), 2.04
(s, 18H, 13-H), 2.31 (s, 9H, 11-H), 6.74 (s, 6H, 12-H), 6.98 (s, 6H, 9-H), 7.09 (s, 3H, 1-
H), 7.77 (d, J = 8.1 Hz, 3H, 8-H), 8.14 (d, J = 8.9 Hz, 3H, 6-H), 8.19 (d, J = 8.9 Hz, 3H,
5-H), 8.65 (d, J = 8.1 Hz, 3H, 7-H), 8.90 (s, 3H, 4-H), 9.57 (s, 3H, 14-H); 13C-NMR
(DMF-d7, 100 MHz): δ = 20.2, 20.4, 21.0, 89.6, 92.7, 114.7, 119.7, 124.5, 125.8, 126.6,
127.6, 128.1, 128.7, 128.9, 132.0, 134.4, 136.1, 137.3, 137.8, 137.9, 139.0, 140.3, 145.7,
146.4, 158.2, 160.9, 162.1; ESI-MS Calcd for [C99H78N6O3+H]+: m/z = 1399.6, Found:
m/z = 1400.0, ESI-MS Calcd for [C99H78N6O3+2H]2+: m/z = 700.3, Found: m/z = 700.5,
ESI-MS Calcd for [C99H78N6O3+3H]3+: m/z = 467.2, Found: m/z = 467.4; Anal Calcd for
C99H78N6O3•3DMF: C, 80.12; H, 6.16; N, 7.79; Found: C, 79.78; H, 6.07; N, 7.64.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
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1.2.2 Synthesis of 1-cyano-4-iododurene (B)
NC17
2 3
4
56
I
B
To a solution of 4.48 g (50.0 mmol) of cuprous cyanide in 100 mL of DMF was added
19.3 g (50.0 mmol) of 1,4-diiododurene and the resultant reaction mixture was heated at
reflux (150-160 °C) for 12 h. Subsequently, the reaction mixture was cooled to room
temperature and a solution of FeCl3 (2.00 g in 1 mL of concentrated HCl and 4 mL of
water) was added. The mixture was heated at 70-80 °C for 20 min and then extracted
with CH2Cl2. The combined extracts were washed with saturated NaCl solution, dried
over MgSO4 and the solvents removed in vacuum. The residue was subjected to column
chromatography (10% EtOAc/hexane, Rf = 0.6) to obtain 11.3 g (39.6 mmol, 79%) of 1-
cyano-4-iododurene as a white solid
MP: 179-180 °C; IR (KBr): ~ν = 2949 (w), 2216 (s), 1545 (m), 1443 (m), 1386 (m), 1258
(m), 1001 (w), 908 (m); 1H-NMR (CDCl3, 400 MHz): δ = 2.51 (s, 6H, 5-H), 2.56 (s, 6H,
6-H); 13C-NMR (CDCl3, 100 MHz): δ = 20.6, 27.6, 114.6, 117.7, 118.2, 137.4, 139.1.
1.2.3 Synthesis of 4-iodo-2,3,5,6-tetramethylbenzaldehyde (C)
I
O
17
2 3
4
56
C 1-Cyano-4-iododurene (5.70 g, 20.0 mmol) was dissolved in 50 mL of dichloromethane
at 0 °C under N2 in a 250 mL round bottom flask, then 22.0 mL of DIBAL (22.0 mmol,
1 M solution in toluene) was added slowly. The reaction mixture was allowed to attain
room temperature and stirred overnight. The reaction mixture was quenched with diluted
HCl, and the contents were heated to reflux for 30 min. Then the reaction mixture was
extracted with CH2Cl2 (2x100 mL), and the combined organic layer was dried over
MgSO4. The crude product was purified by column chromatography (SiO2, hexane:ethyl
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
4
acetate, 100 : 10, Rf = 0.5) to obtain product as a colourless powder in 4.49 g (15.6 mmol,
71%).
MP: 165-167 °C; IR (KBr): ~ν = 2923 (w), 2858 (w), 2742 (w), 1691 (s), 1536 (m), 1442
(w), 1382 (m), 1276 (w), 1063 (w), 918 (m), 672 (w); 1H-NMR (400 MHz, CDCl3):
δ = 2.44 (s, 6H, 5-H), 2.54 (d, J = 4.7 Hz, 6H, 6-H), 10.6 (d, J = 4.7 Hz, 1H, 7-H); 13C-
NMR (100 MHz, CDCl3): δ = 17.6, 27.6, 117.3, 134.3, 135.5, 139.0, 196.6; Anal Calcd
for C11H13IO●0.25H2O: C, 45.15; H, 4.65; Found: C, 45.19; H, 4.27.
1.2.4 Synthesis of 4-(4-iododuryl)-2,2’,6’,2”-terpyridine (D)2
I
NN N
ab
cd
e
f
g
D
Compound C (4.00 g, 13.9 mmol) was dissolved in a solution of NaOH (10.0 g,
250 mmol) in MeOH (500 mL). After stirring for 5 min at room temperature, 2-acetyl-
pyridine (6.06 g, 5.61 ml, 50.0 mmol) was added and the mixture was stirred for 1 h. The
volume of reaction mixture was reduced to about 150 mL, then water (200 mL) was
added and the mixture was extracted with CH2Cl2 (3×100 mL). The organic layers were
dried over MgSO4 and concentrated in vacuum. The solid residue and ammonium acetate
(30.0 g, 390 mmol) were dissolved in EtOH (200 ml) and heated to reflux overnight. The
solution was then cooled, reduced in volume, and water (100 mL) was added. The
mixture was extracted with CH2Cl2 (3×100 ml), and the organic layers were dried over
MgSO4 and concentrated in vacuum. Purification by column chromatography (Al2O3,
CH2Cl2, Rf = 0.9) gave 2.90 g of 4-(4-iododuryl)-2,2’,6’,2”-terpyridine (5.90 mmol, 42%)
as a yellow solid.
MP: 240-242 °C; IR (KBr): ~ν = 3048 (w), 2923 (w), 2920 (w), 2360 (w), 1605 (w), 1584
(s), 1566 (m), 1541 (m), 1465 (s), 1391 (s), 1264 (w), 1214 (w), 1116 (w), 989 (w), 902
(m), 788 (s), 731 (s), 659 (m), 622 (w); 1H-NMR (CDCl3, 400 MHz): δ = 2.08 (s, 6H, f-
H), 2.56 (s, 6H, g-H), 7.31-7.34 (m, 2H, b-H), 7.87 (td, J = 7.8 and 1.6 Hz, 2H, c-H), 8.29
(s, 2H, e-H), 8.66-8.68 (m, 4H, a-, d-H); 13C-NMR (CDCl3, 100 MHz): δ = 20.1, 27.8,
111.6, 121.4, 121.9, 124.0, 131.9, 137.0, 137.7, 140.2, 149.3, 152.6, 155.8, 156.2; ESI-
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
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MS Calcd for [C25H22IN3+H]+: m/z 492.1, Found: m/z 492.0; Anal Calcd for
C25H22IN3●0.5H2O: C, 60.01; H, 4.63; N, 8.40; Found: C, 59.94; H, 4.46; N, 8.17.
1.2.5 Synthesis of tris-terpyridine TT
N
N N
N N
N
N
N
N
abc
d e
f
g
h
TT
Compound D (2.00g, 4.07 mmol), 1,3,5-triethynyl-2,4,6-trimethylbenzene 3 (260 mg,
1.35 mmol) and Pd[(PPh3)4] (230 mg, 200 μmol) were dissolved in dry DMF (50 mL)
and dry triethylamine (50 mL). After deoxygenating the reaction mixture with nitrogen
gas for 15 min., it was heated to 60 °C for 4 hours. Then water (200 mL) was added, and
the mixture was extracted twice with dichloromethane (2x100 mL). The organic layers
were combined and dried over MgSO4. After removal of the solvents, the residue was
purified first by column chromatography on aluminium oxide (CH2Cl2, Rf = 0.5) and
second by recrystallization from chloroform to furnish a light yellow solid (1.52 g,
1.18 mmol, 87%).
MP: >300 ºC; IR (KBr): ~ν = 2920 (w), 2360 (w), 2343 (w), 1604 (w), 1584 (s), 1566 (s),
1543 (m), 1467 (s), 1388 (m), 1263 (w), 1131 (w), 990 (w), 854 (w), 793 (s), 741 (m),
654 (s), 621 (w); 1H-NMR (CDCl3, 400 MHz): δ = 2.08 (s, 18H, f-H), 2.67 (s, 18H, g-H),
3.00 (s, 9H, h-H), 7.34-7.38 (m, 6H, b-H), 7.91 (td, J = 7.8 and 1.6 Hz, 6H, c-H), 8.36 (s,
6H, e-H), 8.71-8.76 (m, 12H, a-, d-H); 13C-NMR (CDCl3, 100 MHz): δ = 18.3, 19.0,
21.3, 95.1, 96.8, 121.4, 122.0, 122.4, 123.7, 123.9, 131.3, 136.2, 137.0, 140.2, 141.7,
149.3, 153.0, 155.8, 156.3; ESI-MS Calcd for [C90H75N9+H]+: m/z 1282.6, Found: m/z
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
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1283.0; ESI-MS Calcd for [C90H75N9+2H]2+: m/z 641.8, Found: m/z 1642.0; Anal Calcd
for C90H75N9●0.5CHCl3: C, 80.98; H, 5.67; N, 9.39; Found: C, 80.91; H, 5.67; N, 9.02.
1.2.6 Synthesis of prism P3
N
N
N
N
OR
OR
N
N N
N N
N
N
N
N
abc
d e
1
9
10
11
12
13
4
5
6
78
f
g
h
The linear bis-phenanthroline BP1 (3.20 mg, 3.34 μmol) and Zn(CF3SO3)2 (2.43 mg,
6.68 μmol) were dissolved slowly in a mixture of dichloromethane/methanol (8.0 mL /
2.0 mL), then the mixture was heated at 40 °C for 5 minutes before a solution of tris-
terpyridine TT (2.86 mg, 2.23 μmol) in dichlorometane (10 mL) was added. After 10 ml
of acetonitrile had been added to this mixture, the mixture was stirred for 30 minutes at
room temperature. The solvents were removed. The residue was analysed by 1H-NMR, 13C-NMR, ESI-MS, and UV/Vis without further purification.
MP: >300 ºC; IR (KBr): ~ν = 2919 (w), 2361 (w), 1614 (s), 1586 (s), 1507 (w), 1458 (m),
1395 (w), 1257 (s), 1260 (s), 1032 (s), 908 (w), 850 (m), 794 (w), 640 (m); 1H-NMR
(CD3CN, 400 MHz): δ = 1.06 (s, 36H, 10-H), 1.26 (s, 54H, 11-, 13-H), 2.18 (s, 36H, g-
H), 2.22 (s, 18H, f1-H), 2.25 (s, 18H, f2-H), 2.99 (s, 18H, h-H), 6.08 (s, 12H, 9-H), 6.28
(s, 12H, 12-H), 6.54 (s, 12H, 1-H), 7.50 (t, J = 6.2 Hz, 12H, b-H), 7.84 (d, J = 6.2 Hz,
12H, a-H), 8.15 (d, J = 8.4 Hz, 6H, 8-H), 8.26 (t, J = 7.8 Hz, 12H, c-H), 8.40 (s, 12H, e-
H), 8.50 (d, J = 9.1 Hz, 6H, 6-H), 8.53 (d, J = 7.8 Hz, 12H, d-H), 8.58 (d, J = 9.1 Hz, 6H,
5-H), 9.09 (s, 6H, 4-H), 9.15 (d, J = 8.4 Hz, 6H, 7-H); 13C-NMR (CD3CN, 100 MHz):
δ = 18.6, 18.7, 18.8, 19.4, 19.5, 19.6, 20.8, 22.2, 88.5, 97.3, 97.6, 99.0, 113.9, 120.1,
122.4, 122.9, 123.3, 124.1, 124.2, 124.8, 125.6, 128.1, 128.2, 128.8, 129.0, 129.3, 130.2,
130.4, 131.6, 132.2, 132.4, 135.5, 135.8, 137.0, 137.4, 138.2, 138.7, 140.3, 140.4, 142.1,
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
7
142.3, 143.2, 143.4, 147.0, 148.1, 150.1, 158.5, 160.4, 161.8, 164.3; ESI-MS Calcd for
[C384H312N30O6Zn6+8OTf]4+ [M-4OTf]4+: m/z 1756.9, Found: m/z 1756.8, ESI-MS Calcd
for [C384H312N30O6Zn6+7OTf]5+ [M-5OTf]5+: m/z 1375.7, Found: m/z 1375.6, ESI-MS
Calcd for [C384H312N30O6Zn6+6OTf]6+ [M-6OTf]6+: m/z 1121.6, Found: m/z 1121.5, ESI-
MS Calcd for [C384H312N30O6Zn6+5OTf]7+ [M-7OTf]7+: m/z 940.1, Found: m/z 939.8,
ESI-MS Calcd for [C384H312N30O6Zn6+4OTf]8+ [M-8OTf]8+: m/z 803.9, Found: m/z
803.7, ESI-MS Calcd for [C384H312N30O6Zn6+3OTf]9+ [M-9OTf]9+: m/z 698.0, Found:
m/z 698.0, ESI-MS Calcd for [C384H312N30O6Zn6+2OTf]10+ [M-10OTf]10+: m/z 613.3,
Found: m/z 613.3; Anal Calcd for C396H312F36N30O42S12Zn6●8CH2Cl2: C, 58.44; H, 3.98;
N, 5.06; S, 4.63; Found: C, 58.20; H, 3.89; N, 5.29; S, 5.01.
1.2.7 Synthesis of prism P4
N
N
O
N
N
O
Fe
Fe
87
6
5
4
N
N N
N N
N
N
N
N
abc
de
1
9
10
11
12
13 f
g
h
14
151617
181920
21
22
The linear bis-phenanthroline BP2 (5.10 mg, 3.34 μmol) and Zn(CF3SO3)2 (2.43 mg,
6.68 μmol) were dissolved slowly in a mixture of dichloromethane/methanol (8.0 mL /
2.0mL). Then the mixture was heated at 40 °C for 5 minutes before a solution of tris-
terpyridine TT (2.86 mg, 2.23 μmol) in dichlorometane (10 mL) was added. After 10 ml
of acetonitrile had been added to this mixture, the mixture was stirred at room
temperature for 30 minutes. The solvents were removed, and the residue was analysed
without further purification by 1H-NMR, 13C-NMR, ESI-MS and UV/Vis.
MP: >300 ºC; IR (KBr): ~ν = 2927 (w), 2361 (w), 1603 (m), 1576 (w), 1260 (s), 1161
(m), 1031 (s), 854 (w), 796 (w), 638 (m); 1H-NMR (CD3CN, 400 MHz): δ = 1.17 (s, 36H,
10-H), 1.26(s, 54H, 11-, 13-H), 1.38 (m, 24H, 16-, 17-H), 1.52 (m, 12H, 18-H), 2.15 (s,
36H, g-H), 2.18 (s, 18H, f1-H), 2.20 (s, 18H, f2-H), 2.28 (m, 12H, 19-H), 2.79 (s, 18H, h-
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
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H), 3.11 (m, 12H, 15-H), 3.59 (m, 12H, 14-H), 4.00 (m, 54H, 20-, 21-, 22-H), 5.96 (s,
12H, 9-H), 6.31 (s, 12H, 12-H), 6.88 (s, 12H, 1-H), 7.51 (t, J = 6.2 Hz, 12H, b-H), 7.80
(d, J = 6.2 Hz, 12H, a-H), 8.18 (d, J = 8.4 Hz, 6H, 8-H), 8.25 (t, J = 8.0 Hz, 12H, c-H),
8.26 (s, 12H, e-H), 8.43 (d, J = 8.0 Hz, 6H, d-H), 8.52 (d, J = 9.1 Hz, 6H, 6-H), 8.58 (d,
J = 9.1 Hz, 6H, 5-H), 9.16 (d, J = 8.4 Hz, 6H, 7-H), 9.18 (s, 6H, 4-H); 13C-NMR
(CD3CN, 100 MHz): δ = 19.0, 19.3, 19.4, 19.6, 19.8, 19.9, 21.1, 22.3, 26.7, 26.9, 30.0,
30.4, 31.5, 68.9, 69.2 (Fc), 69.6 (Fc), 70.8 (Fc), 87.6, 96.8, 97.8, 97.9, 113.4, 120.5,
123.3, 123.4, 123.7, 124.3, 124.4, 125.2, 125.9, 128.6, 129.2, 129.7, 130.0, 130.4, 130.8,
132.2, 132.4, 132.8, 135.8, 136.2, 137.7, 137.8, 138.3, 138.6, 140.8, 140.9, 142.4, 143.3,
143.6, 143.7, 144.0, 147.2, 148.3, 150.4, 160.3 160.7, 162.1, 163.6; ESI-MS Calcd for
[C480H432Fe6N30O6Zn6+7OTf]5+ [M-5OTf]5+: m/z 1697.5, Found: m/z 1697.8, ESI-MS
Calcd for [C480H432Fe6N30O6Zn6+6OTf]6+ [M-6OTf]6+: m/z 1389.8, Found: m/z 1390.0,
ESI-MS Calcd for [C480H432Fe6N30O6Zn6+5OTf]7+ [M-7OTf]7+: m/z 1169.9, Found: m/z
1170.0, ESI-MS Calcd for [C480H432Fe6N30O6Zn6+4OTf]8+ [M-8OTf]8+: m/z 1005.0,
Found: m/z 1004.7, ESI-MS Calcd for [C480H432Fe6N30O6Zn6+3OTf]9+ [M-9OTf]9+: m/z
876.8, Found: m/z 876.6, ESI-MS Calcd for [C480H432Fe6N30O6Zn6+2OTf]10+ [M-
10OTf]10+: m/z 774.2, Found: m/z 774.2; Anal Calcd for
C492H432F36Fe6N30O42S12Zn6●6CH2Cl2: C, 61.39; H, 4.59; N, 4.31; S, 3.95; Found: C,
61.03; H, 4.27; N, 4.00; S, 4.33.
Figure S1. X-ray structure of ligand TP. Three DMF solvate molecules cocrystallised with TP and are bound by hydrogen bonds.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
9
Figure S2. HyperChem® structrue of prism P3. The atoms are colour coded for clarity: carbon: cyan; nitrogen: blue; oxygen: red; zinc: hidden. Left: side view; right: top view.
3.2 nm3.2 nm
0.9 nm
Figure S3. Six ferrocene units represent those in P4. They fill a periodic box of 9216 Å3 as calculated by Hyperchem®. The average distance between every two iron atoms are 2.08 nm.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
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1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0
460
465
470
475
480
485
490
495
R1
P4 L1
L2
E/m
V
Distance (nm)
Figure S4. A plot of ferrocene redox potentials vs. the average distance between ferrocene units of ferrocene containing supramolecular complexes. The supramolecular complexes R1, L1 and L2 were reported earlier.1
-2,0 -1,5 -1,0 -0,5 0,0 0,5 1,0-2,0x10-6
-1,5x10-6
-1,0x10-6
-5,0x10-7
0,0
5,0x10-7
1,0x10-6
I/A
E/V
-0,4 -0,2 0,0 0,2 0,4 0,6 0,8 1,0 1,2
0,0
2,0x10-7
4,0x10-7
6,0x10-7
8,0x10-7
1,0x10-6
I/A
E/V
Figure S5. CV (left: scan rate = 100 mV s-1) and DPV (right: step potential 2 mV) of prism P4 recorded in acetonitrile (0.10 M nBu4NPF6) using DMFc (decamethyl-ferrocene) as internal standard (E1/2 = 0). Peaks at −0.8 V, −0.9 V and −1.2 V are due to the reduction of the phenanthroline and terpyridine units, while the peak at 0.5 V corresponds to the redox potential of the ferrocene units.
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200 250 300 350 400 4500.0
0.2
0.4
0.6
0.8
1.0
Abs
. / a
.u.
Wavelength / nm
BP1BP2TTP3P4
Figure S6. UV-Vis absorption spectra of various ligands (3.0 x 10−6 M in DCM) and complexes (1.0 x 10−6 M in acetonitrile). BP1 and BP2 display broad absorption peaks at 357 and 382 nm that can be assigned to the excitation of the phenylethynyl (p-e) units.4 The p-e absorptions in P3 and P4 are red-shifted by about 20 nm, due to the presence of the phen-Zn(II)-terpy coordination centres at the two termini of BP1 and BP2.
Figure S7. Illustration of the assumed final step of the prism assembly of P3. The atoms are colour coded for clarity: carbon: cyan; nitrogen: blue; oxygen: red; zinc: white. Left: top view; right: side view.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
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method 1
Oligomers P1, P2 P3, P4Oligomers
method 2
intermed.assembly
intermed.assembly
E
Figure S8. Graphical illustration of the final step of the prism assembly along route 1 (left) and 2 (right). Oligomers = mononuclear and oligomeric zinc(II) bisterpyridine complexes.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
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2.
94
47
3.
04
79
3.
06
77
6.
38
42
3.
20
51
2.
92
11
6.
00
80
6.
08
05
9.
00
70
36
.0
00
In
te
gr
al
9.
57
16
8.
90
56
8.
66
26
8.
64
18
8.
20
60
8.
18
39
8.
15
64
8.
13
42
7.
78
37
7.
76
36
7.
08
89
6.
97
81
6.
74
31
2.
31
40
2.
03
94
2.
02
66
( p p m)
1 . 02 . 03 . 04 . 05 . 06 . 07 . 08 . 09 . 0
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :H B 0 8 0 2 3 A
E X P N O : 1
P R O C N O: 1
Figure S9.1H-NMR spectrum of ligand TP.
16
2.
10
02
16
0.
94
35
15
8.
21
88
14
6.
36
03
14
5.
74
34
14
0.
31
96
13
9.
00
01
13
7.
93
76
13
7.
84
34
13
7.
29
50
13
6.
12
12
13
4.
36
47
13
2.
05
12
12
8.
88
95
12
8.
68
39
12
8.
10
98
12
7.
56
15
12
6.
61
89
12
5.
80
50
12
4.
47
69
11
9.
76
43
11
4.
71
76
92
.6
88
5
89
.5
95
4
21
.0
06
22
0.
37
22
20
.1
83
7
( p p m)
1 02 03 04 05 06 07 08 09 01 0 01 1 01 2 01 3 01 4 01 5 01 6 0
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :H B 0 8 0 2 3 A
E X P N O : 1 0
P R O C N O: 1
C 1 3 - N M R
Figure S10. 13C-NMR spectrum of ligand TP.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
14
12
.0
00
5.
26
03
6.
23
89
6.
11
20
9.
10
17
18
.0
10
18
.0
13
In
te
gr
al
8.
75
76
8.
73
82
8.
73
55
8.
72
41
8.
72
21
8.
71
47
8.
71
27
8.
71
00
8.
36
35
7.
93
12
7.
92
65
7.
91
17
7.
90
77
7.
89
22
7.
88
82
7.
37
79
7.
37
53
7.
36
59
7.
36
32
7.
35
98
7.
35
71
7.
34
77
7.
34
50
2.
99
85
2.
66
68
2.
08
48
( p p m)
0 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 09 . 5
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :h b 0 6 0 1 3 a
E X P N O : 1
P R O C N O: 1
h b 0 6 0 1 3 a c d c l 3
t p - p r o t o n C D C l 3 D : o c 1 3
Figure S11. 1H-NMR spectrum of ligand TT.
15
6.
34
81
15
5.
78
26
15
2.
95
50
14
9.
33
92
14
1.
70
49
14
0.
18
83
13
6.
95
80
13
6.
16
12
13
1.
29
44
12
3.
93
42
12
3.
70
29
12
2.
41
77
12
2.
00
64
12
1.
40
66
96
.8
24
29
5.
14
48
21
.3
46
21
8.
98
99
18
.3
30
2
( p p m)
1 02 03 04 05 06 07 08 09 01 0 01 1 01 2 01 3 01 4 01 5 01 6 0
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :h b 0 6 0 1 3 a
E X P N O : 1 0
P R O C N O: 1
h b 0 6 0 1 3 a c d c l 3
t p - C 1 3 ( 1 h o u r ) C D C l 3 D : o c 1 3
Figure S12. 13C-NMR spectrum of ligand TT.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
15
Tris-Phenol-Bis-Terpy-Zn-3#592-607 RT: 10.73-11.14 AV: 16 NL: 6.99E6T: + c Full ms [ 150.00-2000.00]
200 400 600 800 1000 1200 1400 1600 1800 2000m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
1185.1
1184.1
918.7
917.7
753.5
1628.4484.5
739.8
755.61186.9486.4
1501.9920.7429.1 1222.41173.2 1503.11463.71400.2 1985.21151.5
1675.2 1890.31226.3 1615.7947.7 1697.0891.7 1148.9 1759.3641.8426.2 487.7 1228.5
762.7 1118.5689.8573.0383.3868.9355.6
320.8259.5
1501.11501.4150 0.9
1501.8150 0.6
1501.6
1502.1
1502.61500.1
150 2.4150 2.6
1499.6
149 9.9 1503.11499.6
1503.3 150 3.6149 9.1
1499.4
1503.81504.1 150 4.31504.5
150 5.1150 5.3
1,5041,5021,5001,498
100
90
80
70
60
50
40
30
20
10
0
m/ z
1171,511 71,3
1 170,9
1171,11 171,7
1170,7
1171,9
11 72,11 170,5
1172,3
1170,31170,3
1 170,1
117 2,3
1170,1 11 72,5
1172,7
1169,9
1169,7 1173,0
1173,11173,5116 9,3
117 3,4
1169,1
1,1741,1721,1701,168
100
90
80
70
60
50
40
30
20
10
0
M4+M5+
[Zn4(TP)2(BT)2]4+
[Zn4(TP)2(BT)2]3+
[Zn4(TP)2(BT)2]5+
M4+
M5+
[Zn2(BT)]2+[Zn2(BT)2]2+
Figure S13. Top: ESI-MS spectrum of prism P1. Bottom: Theoretical (red) and experimental (black) isotopic distributions of nanoprism P1. For clarity purposes, the counter anion count was omitted in the labeling.
12
.3
32
10
.5
14
16
.2
42
16
.7
71
6.
37
83
21
.3
45
28
.5
39
14
.8
89
27
.3
42
72
.0
00
In
te
gr
al
8.
91
30
8.
81
77
8.
69
34
8.
41
68
8.
16
51
7.
92
07
7.
73
94
7.
58
63
7.
13
11
6.
35
17
6.
09
72
2.
48
52
2.
09
51
1.
87
08
1.
79
10
1.
70
70
1.
61
37
( p p m)
0 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 0
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :h b 0 6 0 6 6 a
E X P N O : 1
P R O C N O: 1
h b 0 6 0 6 6 a
t p - p r o t o n 1 2 8 C D 2 C l 2 D : o c 1 6
Figure S14. 1H-NMR spectrum of prism P1 that is broadened due to rapid equilibration with oligomeric terpyridine complexes.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
16
18
.8
55
40
.3
37
22
.9
11
27
.8
88
25
.6
64
23
.1
71
14
.9
07
35
.7
45
72
.0
00
In
te
gr
al
8.
76
66
8.
62
09
8.
17
04
7.
93
75
7.
90
39
7.
79
31
7.
60
51
7.
10
70
6.
71
22
6.
42
69
6.
11
06
5.
96
70
1.
81
65
1.
62
51
1.
24
91
( p p m)
- 1 . 00 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 08 . 09 . 0
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :h b 0 6 0 6 5 a
E X P N O : 1
P R O C N O: 1
h b 0 6 0 6 5 a
t p - p r o t o n 1 2 8 C D 2 C l 2 D : o c 1 4
Figure S15. 1H-NMR spectrum of prism P2 that is broadened due to rapid equilibration with oligomeric terpyridine complexes..
Prism2-6#1-32 RT: 0.00-0.85 AV: 32 NL: 3.16E7T: + c ms [ 150.00-2000.00]
200 400 600 800 1000 1200 1400 1600 1800 2000m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bun
dan
ce
803.7
698.1
940.5
1121.7
1375.51122.4
613.8
1374.6359.1 699.4 805.8656.1 961.9 1144.7 1409.11366.0361.1 786.7 1021.7612.4 818.0544.1 1237.4 1516.1 1858.21756.71711.2431.9319.1 1966.5287.4
M6+
M5+
M7+
M8+
M9+
M10+
M4+M11+
Figure S16. ESI-MS spectrum of prism P3. For clarity purposes, the counter anion count was omitted in the labeling.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
17
699698697
100
90
80
70
60
50
40
30
20
10
697.7697.8
698.0
698.1
697.9698.2
697.6
698.3
698.2697.4
698.3698.4697.3
698.6
698.6
697.3 698.7
698.7
698.9697.2
697.0 699.0696.9 697.1 699.4696.8
699.1 699.3699.4
696.8 699.5696.6
805804803
100
90
80
70
60
50
40
30
20
10
0
803.4
803.6803.7 803.8
804.1804.0803.5803.2
804.2 804.4
803.1
804.4803.1
802.9803.0
804.7804.6
804.9
804.8802.7
805.3805.2805.1802.6802.3
802.5802.2
939.8
940.0940.3
939.7939.6
940.1939.4
939.3940.4
939.1 940.8940.4
940.7940.6
938.9
938.8941.0
939.0
941.3941.1
938.7 941.5 941.8938.7 941.6 942.1941.7938.5
938.4942.0
942941940939
100
90
80
70
60
50
40
30
20
10
0
1.1241.1231.1221.1211.120
100
90
80
70
60
50
40
30
20
10
0
1121.0
1121.2
1121.51120.8
1121.31122.0
1121.8
1120.7 1122.1
1122.5
1120.51120.3
1122.3
1122.7
1122.81120.2
1120.0
1123.01123.71123.1 1123.3
1119.91119.7 1123.5 1123.7
1119.5
1.3781.3771.3761.3751.3741.373
100
90
80
70
60
50
40
30
20
10
0
1375.0
1376.01375.61375.2 1375.6
1375.41375.0
1374.8 1376.2
1375.81374.6
1376.2
1376.6
1374.4
1376.6
1374.4
1376.81374.0
1377.21373.8
1377.41373.81373.4 1377.8
1378.01373.2 1378.21373.6
1.7601.7581.7561.754
100
90
80
70
60
50
40
30
20
10
0
1756.51757.0
1756.3
1757.51756.0
1755.81755.5
1757.7
1757.8
1755.3
1755.1 1758.21755.0 1758.5
1758.71754.8
1759.21754.6 1759.3
1760.01759.71754.3
1754.01753.5
M5+ M6+
M7+M8+
M4+
M9+
Figure S17. Theoretical (red) and experimental (black) isotopic distributions of nano-prism P3. For clarity purposes, the counter anion count was omitted in the labeling.
6.
81
42
6.
03
28
24
.8
97
11
.8
15
15
.5
44
6.
78
26
16
.3
24
15
.3
92
9.
23
52
12
.0
00
11
.9
37
15
.1
89
14
.1
92
20
.2
40
70
.8
06
42
.9
46
35
.6
50
In
te
gr
al
9.
16
48
9.
14
33
9.
08
62
8.
59
21
8.
56
92
8.
54
17
8.
51
75
8.
49
47
8.
40
01
8.
28
73
8.
26
78
8.
25
10
8.
24
76
8.
16
71
8.
14
63
7.
87
57
7.
85
22
7.
84
01
7.
52
19
7.
50
44
7.
49
03
6.
54
57
6.
28
32
6.
07
57
2.
99
14
2.
84
50
2.
77
86
2.
25
15
2.
21
73
2.
17
97
1.
26
19
1.
06
32
( p p m)
0 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 09 . 51 0 . 0
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :h b 0 6 0 1 6 b
E X P N O : 1
P R O C N O: 1
Figure S18. 1H-NMR spectrum of nanoprism P3.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
18
14
3.
35
36
14
3.
23
37
14
2.
28
26
14
2.
11
98
14
0.
38
90
14
0.
27
76
13
8.
66
68
13
8.
24
69
13
7.
42
44
13
7.
03
02
13
5.
80
50
13
5.
46
22
13
2.
43
76
13
2.
22
34
13
1.
61
51
13
0.
42
41
13
0.
23
56
12
9.
33
59
12
8.
99
32
12
8.
76
18
12
8.
24
77
12
8.
16
20
12
5.
63
44
12
4.
83
76
12
4.
22
06
12
4.
18
64
12
3.
29
53
12
2.
89
26
12
2.
36
99
12
0.
10
79
11
3.
94
73
98
.9
52
89
7.
58
18
97
.2
73
4
88
.4
73
7
22
.2
32
32
0.
83
57
19
.5
76
21
9.
53
33
19
.4
47
61
8.
84
78
18
.6
50
81
8.
63
36
( p p m)
01 02 03 04 05 06 07 08 09 01 0 01 1 01 2 01 3 01 4 01 5 01 6 01 7 0
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :h b 0 6 0 1 6 a
E X P N O : 1 0
P R O C N O: 1
C 1 3 - N M R
Figure S19. 13C-NMR spectrum of prism P3.
Fc-Zn-Prism-1#14-83 RT:0.31-2.13 AV:70 NL:1.85E7T:+ c ms [ 250.00-2000.00]
400 600 800 1000 1200 1400 1600 1800 2000m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
anc
e
1170.0
1390.0
1004.7
1169.1
876.6
1388.7
1696.8
877.5
774.2817.8 1697.8
924.01191.6
1429.7
1430.71155.3 1370.1 1695.4
1709.41013.1990.0655.0 1192.6 1559.61014.1 1712.3624.3 1325.7 1673.7 1860.0432.0 772.8 1731.61324.8
1863.2432.9 1954.8602.2351.1318.9
M5+
M6+
M7+
M8+
M9+
M10+
Figure S20. ESI-MS spectrum of nanoprism P4. For clarity purposes, the counter anion count was omitted in the labeling.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
19
1697,2
1697,0
1697,81697,4
1696,3 1697,51698,2
1696,81696,6
1695,91696,6 1697,9
1696,4
1696,11698,0
1698,4 1699,01695,7
1695,8
1695,4 1698,61698,8
1699,0
1699,1
1699,3
1700,0
1695,3 1699,5
1699,9
1.7001.6991.6981.6971.6961.695
100
90
80
70
60
50
40
30
20
10
1389,1
1389,3 1389,4
1389,6
1389,81389,9
1389,0
1388,8
1390,3
1388,6
1390,1
1390,4
1390,61388,4
1388,31390,8
1388,11388,0
1391,11387,8 1391,4
1390,9
1391,61387,5 1391,9
1392,31387,4 1391,8
1392,1
1387,0
1.3921.3911.3901.3891.388
100
90
80
70
60
50
40
30
20
10
1169,5
1169,4
1169,7
1169,7
1169,81169,3 1169,9
1170,01169,3
1169,31169,0
1170,11169,1 1170,2
1170,4
1168,9
1170,4
1168,8
1170,81170,5
1168,81171,61168,71168,4
1168,7 1170,8
1170,91171,2 1171,5
1168,4 1171,21171,01168,1
1171,4
1168,0
1171,7
1.1721.1711.1701.1691.168
100
90
80
70
60
50
40
30
20
10
0
M5+ M6+ M7+
Figure S21. Theoretical (red) and experimental (black) isotopic distribution of prism P4. For clarity purposes, the counter anion count was omitted in the labeling.
11
.0
23
12
.6
86
11
.1
00
21
.5
05
6.
59
51
4.
40
29
10
.3
19
11
.8
82
12
.0
95
11
.1
84
11
.9
43
54
.0
00
12
.3
92
16
.1
66
12
.3
16
43
.6
18
10
0.
58
88
.0
84
12
4.
49
In
te
gr
al
9.
17
68
9.
17
21
9.
15
13
8.
60
01
8.
57
73
8.
53
23
8.
50
95
8.
43
63
8.
41
62
8.
26
38
8.
25
70
8.
23
76
8.
19
26
8.
17
18
7.
90
99
7.
80
92
7.
79
78
7.
53
13
7.
51
38
7.
50
04
6.
88
07
6.
30
80
5.
96
02
4.
00
18
3.
59
63
3.
57
75
3.
11
22
2.
88
87
2.
77
05
2.
19
58
2.
18
51
2.
17
77
2.
15
22
1.
52
71
1.
40
02
1.
36
06
1.
25
52
1.
17
40
( p p m)
0 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 09 . 51 0 . 0
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :h b 0 7 0 1 1 a
E X P N O : 1
P R O C N O: 1
h b 0 7 0 1 1 a
t p - p r o t o n 1 2 8 C D 3 C N D : o c 1 1 4
Figure S22. 1H-NMR spectrum of nanoprism P4.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008
20
16
3.
64
62
16
2.
13
82
16
0.
72
45
16
0.
30
46
15
0.
45
11
14
8.
33
47
14
7.
22
08
14
3.
98
20
14
3.
72
50
14
3.
63
07
14
3.
32
23
14
2.
41
40
14
0.
92
31
14
0.
78
61
13
8.
60
11
13
8.
27
55
13
7.
84
71
13
7.
67
58
13
6.
15
92
13
5.
79
07
13
2.
71
47
13
2.
38
06
13
2.
23
49
13
0.
77
83
13
0.
43
56
12
9.
96
43
12
9.
73
30
12
9.
20
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( p p m)
02 04 06 08 01 0 01 2 01 4 01 6 01 8 02 0 02 2 0
* * * C u r r e n t D a t a P a r a m e t e r s * * *
N A M E :h b 0 7 0 1 1 c
E X P N O : 1 0
P R O C N O: 1
C 1 3 - N M R
Figure S23. 13C-NMR spectrum of nanoprism P4.
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