Modular synthesis of helicene-like compounds based on the imidazolium motif

Article abstract of DOI:10.1002/ejoc.201402746

Straightforward synthesis of novel mono- and tricationic helical compounds based on the imidazolium core has been developed. The synthetic route based on double [2+2+2] cycloaddition reactions of precursors with the imidazolium core motif is notably modular and reaches beyond established protocols used for the synthesis of imidazolium systems as well as beyond the reported protocols used to assemble compounds with helical frameworks. This approach opens rapid four-step access to a cationic species featuring nine orthoannulated rings that represents the highest order helical nitrogen-based cationic system reported to date.

Full text of DOI:10.1002/ejoc.201402746

Eur. J. Org. Chem. 2014 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014 · ISSN 1099–0690
SUPPORTING INFORMATION
DOI: 10.1002/ejoc.201402746
Title: Modular Synthesis of Helicene-Like Compounds Based on the Imidazolium Motif
Author(s): Martina Čížková, David Šaman, Dušan Koval, Václav Kašička, Blanka Klepetářová, Ivana Císařová, Filip
Teplý*

Table of Contents
1) General Information ................................................................................................. SI 2
2) Materials ................................................................................................................... SI 2
3) Procedures and Analytical Data ............................................................................... SI 4
4) Anion Exchange ....................................................................................................... SI 13
5) Capillary Electrophoresis ......................................................................................... SI 15
6) UV/Vis Absorption and Fluorescence Spectra......................................................... SI 15
7) X-ray Crystallography
SI 15
8) References ................................................................................................................ SI 16
9) 1H and 13C NMR Spectra ......................................................................................... SI 17
SI 1

1) General Information
Liquids and solutions were transferred via needle and syringe under argon atmosphere unless
otherwise stated. Melting points were determined on a Wagner & Munz PolyTherm A micro
melting point apparatus and are uncorrected. Thin-layer chromatography (TLC) analysis was
performed on silica gel plates (Silica gel 60 F254-coated aluminium sheets, Merck, cat. no.
1.05554.0001) and visualized by UV (UV lamp 254/365 nm, Spectroline Model ENF –
240C/FE) and/or chemical staining with KMnO4 [KMnO4 (1% aq), Na2CO3 (2% aq)]. Thin
layer chromatography (TLC) analysis of cationic aromatics was achieved using Stoddart’s
magic mixture[1] (MeOH:NH4Cl (2M aq):MeNO2 7:2:1) as eluent on silica gel plates. Flash
chromatography was performed on silica gel 60 (Fluka, cat. no. 60741) with the indicated
eluent. The CombiFlash Companion automated flash chromatography system with RediSep
silica columns was used in some cases as indicated. Distillation under reduced pressure was
performed in Kugelrohr Glass Drying Oven, Buchi Model B-585. NMR spectra were
measured on Bruker Avance 600 (600 MHz for 1H, 151 MHz for 13C, and 61 MHz for 15N) or
1
13
Bruker Avance 400 (400 MHz for H, 101 MHz for C) NMR spectrometer. Spectra were
referenced relative to the residual peak of CHD2COCD3 (δH = 2.09 ppm), CD3COCD3 (δC =
29.80 ppm), DMSO-d6 (δH = 2.50 ppm, δC = 39.50 ppm), CD3OD (δH = 3.31 ppm, δC = 49.00
ppm). Chemical shifts are given in δ-scale as parts per million (ppm); coupling constants (J)
are given in Hertz. Where indicated, the signal assignments in the NMR spectra are
unambiguous; the numbering scheme is arbitrary and is shown in the inserts. Where assigned,
1
13
all H and C resonance assignments are based on analysis of H,H-COSY, H,H-ROESY,
H,C-HSQC, and H,C-HMBC spectra. IR spectra were recorded on a Bruker EQUINOX55
(IFS55) spectrometer in CHCl3 or as KBr pellets. Abbreviations for intensities of IR bands are
as follows: s for strong, vs for very strong, m for medium, w for weak, vw for very weak.
Mass spectral data were obtained at the Mass Spectrometry Facility operated by the Institute
of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, v.v.i.
ESI mass spectra were recorded using a Thermo Scientific LCQ Fleet mass spectrometer
equipped with an electrospray ion source and controlled by Xcalibur software. The mobile
phase consisted of methanol:water (9:1), flow rate of 200 μL/min. The sample was dissolved,
diluted with the mobile phase and injected using a 5 μL loop. Spray voltage, capillary voltage,
tube lens voltage and capillary temperature were 5.5 kV, 5 V, 80 V, and 275 °C, respectively.
Microwave heated reactions were performed in CEM Discover Apparatus. Caution: the
removal of a solvent in the presence of alkynyl trifluoromethanesulfonate on a rotary
evaporator was always accomplished in a well ventilated fumehood!
2) Materials
Demineralized water was obtained from the Water Purification Facility at the Institute of
Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, v.v.i.
Demineralization was accomplished via filtration through ion exchange columns (Lewatit
S100 for catex column, Lewatit MP500 for anex column) in a demineralization ion exchange
station type ID-PP and IDKP (Kavalier, Votice, Czech Republic). CH2Cl2 and Et3N were
purified via distillation under Ar over CaH2. THF was distilled over Na and benzophenone.
Solvents were degassed before use. Degassed solvents were obtained via the freeze-pump-
thaw method. The solvent was frozen under Ar, and then thawed under vacuum. This process
was repeated 3x. Finally, the thawed solvent was purged with argon. Unless otherwise stated,
all other starting materials and reagents were obtained from commercial suppliers and used
without further purification.
SI 2

Acetone-d6 (Merck, 99.9%, CAS: 666-52-4)
Acetone, dichloromethane, diethyl ether, hexanes, 35% hydrochloric acid (HCl), methanol,
potassium carbonate (K2CO3), potassium chloride (KCl), sodium acetate, sodium hydroxide
(NaOH), and sodium sulfate (Na2SO4) were purchased from Penta, Czech Republic
(www.pentachemicals.eu)
Acetylene (Messer Technogas, dissolved, UN 1001, CAS: 74-86-2)
Argon (Messer Technogas, compressed, UN 1006, CAS: 7440-37-1)
1,2-Bis(diphenylphosphino)ethane (Aldrich, 97%, CAS: 1663-45-2)
[1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II), Pd(dppf)Cl2 (Aldrich, CAS:
72287-26-4)
4-Bromo-1-butyne (Aldrich, 97%, CAS: 38771-21-0)
3-Butyn-1-ol (Alfa Aesar, 98+%, CAS: 927-74-2)
Calcium hydride, CaH2 (Aldrich, 95%, CAS: 7789-78-8)
Chloro(1,5-cyclooctadiene)iridium dimer, [Ir(cod)Cl]2, (Strem Chemicals, 99%, CAS: 12112-
67-3)
Copper iodide, CuI (Alfa Aesar, 98%, Aldrich, 99.99%, CAS: 7681-65-4)
Dicarbonylcyclopentadienyl cobalt, CpCo(CO)2 (Aldrich, CAS: 12078-25-0)
Dichlorobis(triphenylphosphine)palladium, Pd(PPh3)2Cl2 (Aldrich, 99.99%, CAS: 13965-03-
2)
N,N-Dimethylformamide (Aldrich, 99.8%, CAS: 68-12-2)
Dimethyl sulfoxide-d6 (Aldrich, 99.96 %, CAS: 2206-27-1)
Dowex 1x2 chloride form (Supelco, 16-100 mesh, CAS: 69011-19-4)
Ethynylbenzene (Aldrich, 98%, CAS: 536-74-3)
2-Ethynylpyridine (Aldrich, 98%, CAS: 1945-84-2)
Highly sulfated γ-cyclodextrin (Beckman Coulter, Brea, CA, USA, S 808064)
Imidazole (Aldrich, ≥99.5%, CAS: 288-32-4)
Iodine monochloride, ICl (Aldrich, 98%, CAS: 7790-99-0)
Methanol (Aldrich, ≥99.9%, CAS: 67-56-1)
Methanol-d4 (Aldrich, 99.96 %, CAS: 811-98-3)
2,5-Norbornadiene (Alfa Aesar, CAS: 121-46-0)
Palladium 10% on carbon, [Pd/C] (Alfa Aesar)
Pyridine (Alfa Aesar, anhydrous 99.5+%, Lachner, CAS: 110-86-1)
Sodium iodide, NaI (Aldrich, ≥99%, CAS: 7681-82-5)
Sodium sulfate, Na2SO4 (Riedel-de Haën, anhydrous, CAS: 7757-82-6)
Tetrahydrofuran (Aldrich, ≥99.5%, CAS: 109-99-9)
Tetrakis(triphenylphosphine)palladium, Pd(PPh3)4 (Alfa Aesar, 99.8%, CAS: 14221-01-3)
Triethylamine (Alfa Aesar, 99%, CAS: 121-44-8)
Trifluoromethanesulfonic anhydride (Alfa Aesar, 98%, Acros Organics, 98+%, CAS: 358-23-
6)
Triphenylphosphine (Alfa Aesar, 99%, Aldrich, ≥95.0%, CAS: 603-35-0)
Tris(triphenylphosphine)rhodium chloride, RhCl(PPh3)3 (Fluka, 97+%, Aldrich, CAS: 14694-
95-2)
SI 3

3) Procedures and Analytical Data
4,5-Diiodo-1H-imidazole (5)
CAS: 15813-09-9
Based on a literature procedure.[2]
A solution of KCl (1.79 g, 23.97 mmol, 4 eq) in H2O (7 mL) was added to a flask containing
ICl (2.33 g, 14.34 mmol, 2.4 eq) under Ar. The resulting solution was added dropwise to a
solution of imidazole (404 mg, 5.93 mmol, 1 eq) in H2O (5 mL) under Ar. The heterogeneous
mixture was stirred at room temperature for 22 h. Then, a solution of 2M aq NaOH (12 mL)
was added to dissolve most of the solids. The resulting suspension was filtered and pH of the
solution was then adjusted to 9.5 by addition of conc. HCl (0.5 mL). White solids precipitated
and the suspension was stirred at room temperature for next 2 h. The suspension was
centrifuged and the liquid was decanted. The solids were washed with H2O. Product 5 was
isolated as a white solid in 63 % yield (1.19 g, 3.71 mmol).
1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 7.84 (s, 1H, H-1). 13C NMR (151
~
MHz, (CD3)2CO): δ (ppm) = 142.19 (C-1), C-2 not observed. IR (KBr): (cm-

1) = 620 w, 654 m, 818 m, 921 w, 954 vs, 1152 m, 1179 m, 1271 w, 1285 m,
1440 w, 1541 w, 1812 w, 2650 m, 3115 w. MS (ESI) m/z (%): 321 [M+H+]
(100). HRMS (ESI) m/z: [M+H+] (C3H3I2N2) calc.: 320.8380, found: 320.8380.
m.p. = 196 - 198 °C (acetone).
4,5-Bis(phenylethynyl)-1H-imidazole (7)
Entry
Pd catalyst
Solvent
MW
T
[°C]
60
100
100
100
100
100
t
[h]
17
1
1
1
Yield
[%]a
24
49
42
46
59
66
1
2
3
4
5
6
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(dppf)
Pd/C, PPh3
Pd(PPh3)4
THF
DMF
DMF
H2O
DMF
DMF
no
yes
yes
yes
yes
no
1
1.5
Pd(PPh3)4
aIsolated yields; dppf = 1,1'-bis(diphenylphosphino)ferrocene.
SI 4

Method 1 (Table 1, entry 1): Diiodoimidazole 5 (71 mg, 0.22 mmol, 1 eq), CuI (5 mg, 0.03
mmol, 12 mol%), and PdCl2(PPh3)2 (17 mg, 0.02 mmol, 11 mol%) were placed to a Schlenk
tube, which was then purged with Ar (3x). THF (5 mL), phenylacetylene (6) (100 μL, 0.91
mmol, 4.1 eq), and Et3N (120 μL, 0.86 mmol, 3.9 eq) were then added. The mixture was
stirred at 60 °C for 17 h. After cooling to room temperature, the volatiles were removed on a
rotary evaporator and the resultant residue was purified by flash chromatography on silica gel
(column diameter 1.5 cm, plug height 7 cm, hexane:EtOAc 1:2). Product 7 was isolated as a
yellow solid in 24 % yield (14 mg, 0.05 mmol).
Method 2 (Table 1, entry 2): Diiodoimidazole 5 (71 mg, 0.22 mmol, 1 eq), CuI (6 mg, 0.03
mmol, 15 mol%), and PdCl2(PPh3)2 (23 mg, 0.03 mmol, 15 mol%) were placed to a reaction
vessel, which was then purged with Ar (3x). DMF (4 mL), phenylacetylene (6) (100 μL, 0.91
mmol, 4.1 eq), and Et3N (250 μL, 1.79 mmol, 8.1 eq) were then added. The mixture was
stirred at 100 °C for 1 h under microwave irradiation (100 W, 100 psi). The volatiles were
removed on a rotary evaporator and the resultant residue was purified by flash
chromatography on silica gel (column diameter 2.5 cm, plug height 7 cm, hexane:EtOAc 1:1 -
0:1). Product 7 was isolated as a yellow solid in 49 % yield (30 mg, 0.11 mmol).
Method 3 (Table 1, entry 3): Diiodoimidazole 5 (103 mg, 0.32 mmol, 1 eq), CuI (5 mg, 0.03
mmol, 7 mol%), and PdCl2(dppf) (11 mg, 0.02 mmol, 5 mol%) were placed to a reaction
vessel, which was then purged with Ar (3x). DMF (6 mL), Et3N (300 μL, 2.15 mmol, 6.7 eq),
and phenylacetylene (6) (170 μL, 1.55 mmol, 4.8 eq) were then added. The mixture was
stirred at 100 °C for 1 h under microwave irradiation (100 W, 100 psi). The volatiles were
removed on a rotary evaporator and the resultant residue was purified by flash
chromatography on silica gel (column diameter 2.5 cm, plug height 8 cm, hexane:EtOAc 1:2).
Product 7 was isolated as a yellow liquid in 42 % yield (36 mg, 0.14 mmol).
Method 4 (Table 1, entry 4): Diiodoimidazole 5 (103 mg, 0.32 mmol, 1 eq), CuI (8 mg, 0.04
mmol, 13 mol%), PPh3 (31 mg, 0.12 mmol, 37 mol%), and 10 % Pd/C (40 mg, 0.04 mmol, 12
mol%) were placed to a reaction vessel, which was then purged with Ar (3x). H2O (6 mL),
Et3N (300 μL, 2.15 mmol, 6.7 eq), and phenylacetylene (6) (170 μL, 1.55 mmol, 4.8 eq) were
then added. The mixture was stirred at 100 °C for 1 h under microwave irradiation (100 W,
100 psi). The volatiles were removed on a rotary evaporator and the resultant residue was
purified by flash chromatography on silica gel (column diameter 2.5 cm, plug height 8 cm,
hexane:EtOAc 1:2). Product 7 was isolated as a yellow liquid in 46 % yield (40 mg, 0.15
mmol).
Method 5 (Table 1, entry 5): Diiodoimidazole 5 (100 mg, 0.31 mmol, 1 eq), CuI (13 mg, 0.07
mmol, 22 mol%), and Pd(PPh3)4 (36 mg, 0.03 mmol, 10 mol%) were placed to a reaction
vessel, which was then purged with Ar (3x). DMF (6 mL), Et3N (300 μL, 2.15 mmol, 6.9 eq),
and phenylacetylene (6) (170 μL, 1.55 mmol, 5.0 eq) were then added. The mixture was
stirred at 100 °C for 1 h under microwave irradiation (100 W, 100 psi). The volatiles were
removed on a rotary evaporator and the resultant residue was purified by flash
chromatography on silica gel (column diameter 2.5 cm, plug height 8 cm, hexane:EtOAc 1:2).
Product 7 was isolated as a yellow solid in 59 % yield (50 mg, 0.19 mmol).
Method 6 (Table 1, entry 6): Diiodoimidazole 5 (107 mg, 0.33 mmol, 1 eq), CuI (6 mg, 0.03
mmol, 10 mol%), and Pd(PPh3)4 (19 mg, 0.02 mmol, 5 mol%) were placed to a Schlenk tube,
which was then purged with Ar (3x). DMF (6 mL), Et3N (300 μL, 2.15 mmol, 6.5 eq), and
phenylacetylene (6) (170 μL, 1.55 mmol, 4.7 eq) were then added. The mixture was stirred at
100 °C for 1.5 h. After cooling to room temperature, the volatiles were removed on a rotary
evaporator and the resultant residue was purified by flash chromatography on silica gel
(column diameter 2.5 cm, plug height 11 cm, hexane:EtOAc 1:1). Product 7 was isolated as a
yellow solid in 66 % yield (59 mg, 0.22 mmol).
SI 5

1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 7.44 - 7.50 (m, 6H, H-7,
13
H-8); 7.58 - 7.62 (m, 4H, H-6); 7.84 (s, 1H, H-1). C NMR (151
MHz, (CD3)2CO): δ (ppm) = 123.61 (C-5), 129.51 (C-7, C-8), 132.03
~
(C-6), 137.68 (C-1), C-2, C-3, C-4 not observed. IR (CHCl3): (cm-

1) = 451 w, 510 w, 526 w, 534 w, 564 m, 629 w, 641 w, 690 vs, 835
w, 915 w, 944 w, 999 vw, 1028 w, 1071 m, 1122 w, 1161 w, 1174 w,
1188 m, 1261 w, 1300 w, 1329 vw, 1372 w, 1443 m, 1476 m, 1489 m,
1498 w, 1555 w, 1573 w, 1599 m, 2214 w, 2232 w, 3042 m, 3065 m, 3083 m, 3128 m, 3444
m. MS (ESI) m/z (%): 269 [M+H+] (100). HRMS (ESI) m/z: [M+H+] (C19H13N2) calc.:
269.1073, found: 269.1074. m.p. = 63 - 65 °C (hexane/EtOAc).
1-(But-3-ynyl)-4,5-bis(phenylethynyl)-1H-imidazole (10)
Method 1 (using bromobutyne 8): Bis(phenylethynyl)imidazole 7 (47 mg, 0.18 mmol, 1 eq)
and K2CO3 (82 mg, 0.59 mmol, 3.4 eq) were placed to a round-bottomed flask, which was
then purged with Ar (3x). DMF (4 mL) and bromobutyne 8 (25 μL, 0.27 mmol, 1.5 eq) were
then added. The mixture was stirred at 80 °C for 18 h. After cooling to room temperature, the
volatiles were removed on a rotary evaporator and the resultant residue was purified by flash
chromatography on silica gel (column diameter 1.5 cm, plug height 6 cm, hexane:EtOAc 1:1).
Product 10 was isolated as a yellow liquid in 41 % yield (23 mg, 0.07 mmol).
Method 2 (using butynyl trifluoromethanesulfonate 9): Bis(phenylethynyl)imidazole 7 (50
mg, 0.19 mmol, 1 eq) and K2CO3 (105 mg, 0.76 mmol, 4.1 eq) were placed to a round-
bottomed flask, which was then purged with Ar (3x). DMF (4 mL) and butynyl triflate 9 (141
mg, 0.70 mmol, 3.8 eq) were then added. The mixture was stirred at 90 °C for 17 h. After
cooling to room temperature, the solvent was removed on a rotary evaporator and the resultant
residue was purified by flash chromatography on silica gel (column diameter 2.5 cm, plug
height 9 cm, hexane:EtOAc 1:1). Product 10 was isolated as yellow liquid in 80 % yield (47
mg, 0.15 mmol).
1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 2.58 (t, J = 2.7 Hz,
1H, H-9); 2.90 (dt, J = 2.7, 6.7 Hz, 2H, H-7); 4.41 (t, J = 6.7 Hz,
2H, H-6); 7.43 - 7.52 (m, 6H, H-14, 15, 20, 21); 7.60 - 7.62 (m,
2H, H-13); 7.65 - 7.68 (m, 2H, H-19); 7.85 (s, 1H, H-1). 13C NMR
(151 MHz, (CD3)2CO): δ (ppm) = 20.90 (C-7), 45.53 (C-6), 72.64
(C-9), 77.41 (C-10), 80.73 (C-8), 84.13 (C-11), 92.38 (C-16),
100.42 (C-17), 119.77 (C-4), 123.06 (C-18), 123.93 (C-12),
129.32 (C-15), 129.47 (C-14), 129.60 (C-20), 129.82 (C-3),
~
129.96 (C-21), 132.09 (C-13), 132.10 (C-19), 139.90 (C-1). IR (CHCl3): (cm-1) = 526 m,

534 w, 645 s, 690 vs, 840 w, 917 w, 999 w, 1029 w, 1070 w, 1172 w, 1263 m, 1278 m, 1319
w, 1431 w, 1444 m, 1486 vs, 1544 w, 1573 w, 1599 m, 2125 vw, 2208 w, 2223 w, 3040 w,
SI 6

3066 w, 3084 w, 3119 w, 3308 s. MS (ESI) m/z (%): 321 [M+H+] (100). HRMS (ESI) m/z:
[M+H+] (C23H17N2) calc.: 321.1386, found: 321.1386.
1,3-Di(but-3-ynyl)-4,5-bis(phenylethynyl)-1H-imidazol-3-ium trifluoromethanesulfonate
(3)
Substituted imidazole 10 (118 mg, 0.37 mmol, 1 eq) was placed to a round-bottomed flask,
which was then purged with Ar (3x). CH2Cl2 (8 mL) and butynyl triflate 9 (368 mg, 1.82
mmol, 5 eq) were added. The mixture was stirred at 40 °C for 19 h. After cooling to room
temperature, the volatiles were removed on a rotary evaporator. The resultant residue was
sonicated with Et2O, the suspension was then centrifuged, and the liquid was decanted. The
residue was washed with Et2O (2x). Product 3 was isolated as a white solid in 92 % yield (177
mg, 0.34 mmol).
1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 2.79 (t, J = 2.7 Hz, 2H,
H-12); 3.10 (dt, J = 2.7, 6.4 Hz, 4H, H-10); 4.82 (t, J = 6.4 Hz, 4H,
H-9); 7.56 - 7.60 (m, 4H, H-7); 7.62 - 7.66 (m, 2H, H-8); 7.79 -
13
7.82 (m, 4H, H-6); 9.61 (s, 1H, H-1). C NMR (151 MHz,
(CD3)2CO): δ (ppm) = 20.07 (C-10), 48.46 (C-9), 73.14 (C-3),
74.21 (C-12), 79.37 (C-11), 103.85 (C-4), 120.73 (C-5), 121.42
(C-2), 129.81 (C-7), 131.65 (C-8), 132.83 (C-6), 138.69 (C-1). IR
~
(CHCl3): (cm-1) = 519 w, 575 w, 638 s, 688 m, 918 w, 1000 w,

1030 vs, 1070 vw, 1156 m, 1167 m, 1258 s, 1282 s, 1429 w, 1444 w, 1489 w, 1498 w, 1555
w, 1583 w, 1609 w, 2128 vw, 2216 w, 2228 w, 3119 w, 3309 m. MS (ESI) m/z (%): 373 [M-
TfO-] (100). HRMS (ESI) m/z: [M-TfO-] (C27H21N2) calc.: 373.1699, found: 373.1699. m.p.
= 107 - 109 °C (CH2Cl2/Et2O).
Helical monocation 1
Method 1 (Table 2, entry 5): Tetrayne 3 (16 mg, 0.03 mmol, 1 eq) was placed to a reaction
vessel, which was then purged with Ar (3x). DMF (2 mL), norbornadiene (18 μL, 16 mg, 0.18
SI 7

mmol, 5.9 eq, ρ = 0.906 g/mL), and CpCo(CO)2 (4 μL, 5 mg, 0.03 mmol, 1 eq, ρ = 1.35
g/mL) were added. The mixture was stirred at 180 °C for 1 h under microwave irradiation
(100 W, 50 psi). The solvent was removed on a rotary evaporator and the resultant residue
was purified by flash chromatography on silica gel (column diameter 1.5 cm, plug height 8
cm, CH2Cl2:MeOH 15:1). The compound 1 was isolated as a yellowish solid in 71 % yield
(12 mg, 0.02 mmol).
Method 2 (Table 2, entry 4): Tetrayne 3 (11 mg, 0.02 mmol, 1 eq) was placed to a reaction
vessel, which was then purged with Ar (3x). DMF (2 mL) and CpCo(CO)2 (3 μL, 4mg, 0.02
mmol, 1.1 eq, ρ = 1.35 g/mL) were added. Acetylene gas was bubbled through the mixture for
5 min. The mixture was then stirred at 150 °C for 0.5 h under microwave irradiation (30 W,
30 psi). The solvent was removed on a rotary evaporator and the resultant residue was
purified by flash chromatography on silica gel (column diameter 1.5 cm, plug height 9 cm,
CH2Cl2:MeOH 15:1). The compound 1 was isolated as a yellowish solid in 76 % yield (9 mg,
0.02 mmol).
1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 2.93 (ddd, J = 4.8, 13.6,
15.5 Hz, 2H, H-5); 3.10 (ddd, J = 1.8, 3.1, 15.5 Hz, 2H, H-5); 4.12 (ddd,
J = 3.1, 12.7, 13.6 Hz, 2H, H-4); 4.85 (ddd, J = 1.8, 4.8, 12.7 Hz, 2H, H-
4); 6.92 (tt, J = 1.3, 7.7 Hz, 2H, H-15); 7.01 - 7.05 (m, 4H, H-14); 7.08
(dt, J = 1.2, 7.4 Hz, 2H, H-11); 7.14 (dt, J = 1.1, 7.8 Hz, 2H, H-9); 7.18 -
7.22 (m, 4H, H-13); 7.30 (t, J = 7.6 Hz, 2H, H-10); 9.45 (bs, 1H, H-3).
13C NMR (151 MHz, (CD3)2CO): δ (ppm) = 30.90 (C-5), 44.82 (C-4),
123.92 (C-7), 126.73 (C-2, C-11), 128.24 (C-15), 128.63 (C-14), 129.21
(C-13), 129.98 (C-9), 130.43 (C-10), 134.83 (C-3), 138.23 (C-6), 140.01
~
(C-12), 141.68 (C-8). IR (CHCl3): (cm-1) = 518 w, 574 w, 638 s, 699 s, 917 vw, 1001 vw,

1030 vs, 1074 w, 1167 m, 1229 m, 1261 s, 1279 s, 1433 w, 1444 w, 1461 w, 1469 vw, 1476
w, 1490 vw, 1499 w, 1549 w, 1574 w, 1586 w, 1594 vw, 1602 w, 2856 w, 2931 w, 3062 w,
3110 w. MS (ESI) m/z (%): 425 [M-TfO-] (100). HRMS (ESI) m/z: [M-TfO-] (C31H25N2)
calc.: 425.2012, found: 425.2013. m.p. = 123 - 125 °C (CH2Cl2).
2-(But-3-ynyl)-10-phenyl-1-(phenylethynyl)-5,6-dihydroimidazo[5,1-a]isoquinolin-2-ium
trifluoromethanesulfonate (14)
Method 1 (Table 2, entry 1): Tetrayne 3 (16 mg, 0.03 mmol, 1 eq) and RhCl(PPh3)3 (3 mg,
3.1 μmol, 11 mol%) were placed to a Schlenk tube, which was purged with Ar (3x). DMF (2
mL) was added and Ar atmosphere was changed to an atmosphere of acetylene (a balloon).
The reaction mixture was stirred at 80 °C for 2 h. After cooling to room temperature, the
mixture was concentrated in vacuo and the resultant residue was purified by flash
chromatography on silica gel (column diameter 0.5 cm, plug height 7 cm, CH2Cl2:MeOH
10:1). Product 14 was isolated as a brownish oil in 41 % yield (7 mg, 0.01 mmol).
SI 8

Method 2 (Table 2, entry 2): Tetrayne 3 (11 mg, 0.02 mmol, 1 eq) and RhCl(PPh3)3 (2 mg,
1.6 μmol, 8 mol%) were placed to a reaction vessel, which was then purged with Ar (3x).
DMF (2 mL) was then added. Acetylene was bubbled through the mixture for 5 min. The
mixture was then stirred at 140 °C for 0.5 h under microwave irradiation (30 W, 30 psi). The
volatiles were removed on a rotary evaporator and NMR was recorded using crude product.
Method 3 (Table 2, entry 3): Tetrayne 3 (21 mg, 0.04 mmol, 1 eq), dppe (3 mg, 7.8 μmol, 20
mol%), and [Ir(cod)Cl]2 (3 mg, 4.8 μmol, 12 mol%) were placed to a Schlenk tube, which was
then purged with Ar (3x). DMF (2 mL) was added and Ar atmosphere was changed to an
atmosphere of acetylene (a balloon). The reaction mixture was stirred at 130 °C for 17 h.
After cooling to room temperature, the volatiles were removed on a rotary evaporator and
NMR was recorded using crude product.
1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 2.68 (t, J = 2.7 Hz, 1H,
H-17); 2.90 (dt, J = 2.7, 6.7 Hz, 2H, H-15); 3.39 (m, 2H, H-7);
4.56 (t, J = 6.7 Hz, 2H, H-14); 4.76 (m, 2H, H-6); 7.23 - 7.26 (m,
1H, H-21); 7.31 - 7.34 (m, 2H, H-26); 7.43 - 7.46 (m, 2H, H-25);
7.46 - 7.49 (m, 2H, H-20); 7.50 - 7.53 (m, 1H, H-27); 7.53 (bdd, J
= 1.4, 7.8 Hz, 1H, H-11); 7.56 (ddt, J = 0.9, 1.4, 7.6 Hz, 1H, H-9);
7.59 - 7.61 (m, 2H, H-19); 7.65 (t, J = 7.7 Hz, 1H, H-10); 9.52 (s,
1H, H-5). 13C NMR (151 MHz, (CD3)2CO): δ (ppm) = 20.18 (C-
15), 30.37 (C-7), 45.10 (C-6), 47.44 (C-14), 73.65 (C-17), 74.13 (C-22), 79.47 (C-16), 103.41
(C-23), 115.06 (C-3), 121.70 (C-18), 121.85 (C-13), 128.35 (C-9), 128.39 (C-21), 129.34 (C-
20), 129.77 (C-19), 130.16 (C-26), 130.76 (C-27), 131.63 (C-10), 131.73 (C-11), 132.37 (C-
~

2), 132.60 (C-25), 136.84 (C-5), 138.38 (C-8), 141.37 (C-24), 141.81 (C-12). IR (CHCl3):
(cm-1) = 518 m, 574 m, 638 vs, 648 s, 689 s, 700 s, 710 w, 917 w, 1000 w, 1030 vs, 1071 w,
1075 w, 1091 vw, 1171 s, 1228 s, 1259 vs, 1279 vs, 1358 m, 1430 m, 1436 m, 1444 m, 1459
m, 1473 m, 1493 m, 1498 w, 1557 m, 1574 m, 1592 m, 1605 w, 2126 vw, 2223 w, 2855 w,
2928 w, 2966 m, 3026 s, 3062 m, 3088 m, 3128 m, 3309 m, MS (ESI) m/z (%): 399 [M-TfO-
] (100). HRMS (ESI) m/z: [M-TfO-] (C29H23N2) calc.: 399.1856, found: 399.1854.
2,2'-(1H-Imidazole-4,5-diyl)bis(ethyne-2,1-diyl)dipyridine (12)
Diiodoimidazole 5 (642 mg, 2.01 mmol, 1 eq), CuI (38 mg, 0.20 mmol, 10 mol%), and
Pd(PPh3)4 (115 mg, 0.10 mmol, 5 mol%) were placed to a Schlenk tube, which was then
purged with Ar (3x). DMF (48 mL), ethynylpyridine 11 (810 μL, 8.02 mmol, 4 eq), and Et3N
(2 mL) were then added. The mixture was stirred at 60 °C for 18 h. After cooling to room
temperature, the volatiles were removed on a rotary evaporator and the resultant residue was
purified by chromatography on silica gel (2 x 40 g) in two portions using a CombiFlash
apparatus (0 - 30 min, 0 - 5 % MeOH in CH2Cl2, 30 - 45 min, 5 % MeOH in CH2Cl2, 45 - 60
min, 5 - 50 % MeOH in CH2Cl2). Fractions containing the product were collected and the
solvent was removed on a rotary evaporator. The mixture was then sonicated with
SI 9

EtOAc:acetone 3:1, centrifuged, and the liquid was decanted. The mixture was then washed
with EtOAc. Product 12 was isolated as a grey solid in 63 % yield (343 mg, 1.27 mmol).
1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 7.43 (bdd, J = 4.8, 7.6
Hz, 2H, H-5); 7.70 (dt, J = 1.1, 7.8 Hz, 2H, H-3); 7.88 (dt, J = 1.7, 7.7
Hz, 2H, H-4); 7.92 (s, 1H, H-10); 8.66 (ddd, J = 1.0, 1.7, 4.8 Hz, 2H,
13
H-6). C NMR (151 MHz, (CD3)2CO): δ (ppm) = 124.12 (C-5),
128.04 (C-3), 137.25 (C-4), 138.38 (C-10), 143.79 (C-2), 151.09 (C-
~
6), C-7, C-8, C-9 not observed. IR (CHCl3): (cm-1) = 400 w, 621

w, 638 w, 944 w, 992 w, 1046 w, 1093 w, 1110 w, 1151 m, 1264 m,
1426 s, 1438 m, 1466 s, 1486 m, 1494 m, 1552 w, 1563 m, 1586 vs,
2218 m, 2239 w, 3060 m, 3084 m, 3127 w, 3439 w. MS (ESI) m/z (%): 271 [M+H+] (100).
HRMS (ESI) m/z: [M+H+] (C17H11N4) calc.: 271.0978, found: 271.0978. m.p. = 176 -
178 °C (EtOAc/acetone).
2,2'-(1-(But-3-ynyl)-1H-imidazole-4,5-diyl)bis(ethyne-2,1-diyl)dipyridine (13)
Bis(pyridylethynyl)imidazole 12 (69 mg, 0.26 mmol, 1 eq) and K2CO3 (137 mg, 0.99 mmol,
3.9 eq) were placed to a Schlenk tube, which was then purged with Ar (3x). DMF (5 mL) and
butynyl triflate 9 (216 mg, 1.07 mmol, 4.2 eq) were then added. The mixture was stirred at
90 °C for 24 h. After cooling to room temperature, the solvent was removed on rotary
evaporator and the residue was mixed with EtOAc and extracted with H2O (3x). EtOAc layer
was dried with anhydrous Na2SO4. The volatiles were removed on a rotary evaporator and the
resultant residue was purified by flash chromatography on silica gel (column diameter 1.5 cm,
plug height 14 cm, hexane:EtOAc 1:4 - 0:1). Product 13 was isolated as a yellowish oil in
72 % yield (60 mg, 0.19 mmol).
1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 2.58 (t, J = 2.7 Hz, 1H,
H-25); 2.92 (dt, J = 2.7, 6.6 Hz, 2H, H-23); 4.44 (t, J = 6.6 Hz, 2H,
H-22); 7.41 (ddd, J = 1.2, 4.8, 7.6 Hz, 1H, H-19); 7.46 (ddd, J =
1.2, 4.8, 7.6 Hz, 1H, H-11); 7.69 (dt, J = 1.1, 7.8 Hz, 1H, H-17);
7.77 (dt, J = 1.1, 7.8 Hz, 1H, H-9); 7.88 (dt, J = 1.8, 7.7 Hz, 1H,
H-18); 7.91 (dt, J = 1.8, 7.7 Hz, 1H, H-10); 7.93 (s, 1H, H-2); 8.65
(ddd, J = 1.0, 1.8, 4.8 Hz, 1H, H-20); 8.68 (ddd, J = 1.0, 1.8, 4.8
Hz, 1H, H-12). 13C NMR (151 MHz, (CD3)2CO): δ (ppm) = 20.86
(C-23), 45.68 (C-22), 72.76 (C-25), 76.22 (C-14), 80.61 (C-24), 82.94 (C-6), 92.58 (C-15),
100.46 (C-7), 119.95 (C-4), 123.96 (C-19), 124.47 (C-11), 128.05 (C-17), 128.22 (C-9),
130.09 (C-5), 137.18 (C-18), 137.34 (C-10), 140.61 (C-2), 143.31 (C-8), 144.01 (C-16),
~
151.05 (C-20), 151.20 (C-12). IR (CHCl3): (cm-1) = 400 w, 629 w, 646 m, 658 m, 828 w,

890 vw, 991 w, 1047 w, 1092 w, 1151 m, 1270 m, 1321 w, 1427 s, 1431 m, 1447 w, 1461 s,
SI 10

1469 vs, 1492 w, 1543 w, 1563 m, 1585 s, 2125 vw, 2218 w, 2225 w, 2236 w, 3057 w, 3084
vw, 3123, 3309 m. MS (ESI) m/z (%): 322 [M+] (95), 321 (100), 294 (50), 244 (20). HRMS
(ESI) m/z: [M+] (C21H14N4) calc.: 322.1218, found: 322.1216.
2,2'-(1,3-Di(but-3-ynyl)-1H-imidazole-3-ium-4,5-diyl)bis(ethyne-2,1-diyl)bis(1-(but-3-
ynyl)pyridinium) trifluoromethanesulfonate (4)
Substituted imidazole 13 (42 mg, 0.13 mmol, 1 eq) was placed to a round-bottomed flask,
which was then purged with Ar (3x). CH2Cl2 (3 mL) and butynyl triflate 9 (124 mg, 0.61
mmol, 4.8 eq) were added. The mixture was stirred at 40 °C for 22 h. After cooling to room
temperature, Et2O (2 mL) was added. The mixture was then sonicated, the resulting
suspension was then centrifuged, and the liquid was decanted. The solid residue was washed
with CH2Cl2: Et2O 1:1 (2x) and Et2O (2x). Product 4 was isolated as a brownish solid in 95 %
yield (114 mg, 0.12 mmol).
1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 2.77 (t, J = 2.7
Hz, 2H, H-15); 2.80 (t, J = 2.7 Hz, 2H, H-19); 3.14 (dt, J =
2.7, 6.5 Hz, 4H, H-17); 3.27 (dt, J = 2.7, 6.6 Hz, 4H, H-13);
4.94 (t, J = 6.5 Hz, 4H, H-16); 5.32 (t, J = 6.6 Hz, 4H, H-12);
8.47 (ddd, J = 1.6, 6.2, 7.7 Hz, 2H, H-9); 8.85 (ddd, J = 0.6,
1.6, 8.0 Hz, 2H, H-11); 8.91 (dt, J = 1.4, 7.9 Hz, 2H, H-10);
9.43 (ddd, J = 0.6, 1.4, 6.2 Hz, 2H, H-8); 9.89 (s, 1H, H-1).
13C NMR (151 MHz, (CD3)2CO): δ (ppm) = 20.41 (C-17),
20.90 (C-13), 49.69 (C-16), 60.00 (C-12), 74.74 (C-19), 75.36 (C-15), 79.13 (C-14), 79.45
(C-18), 86.69 (C-4), 92.73 (C-5), 122.54 (C-3), 130.09 (C-9), 135.24 (C-11), 135.89 (C-6),
~
141.67 (C-1), 147.33 (C-10), 148.79 (C-8). IR (KBr): (cm-1) = 518 m, 574 m, 638 s, 733

vw, 757 w, 781 w, 1031 s, 1163 s, 1226 m, 1262 vs, 1276 vs, 1351 w, 1435 w, 1466 w, 1509
w, 1518 w, 1556 vw, 1576 w, 1619 m, 2122 w, 2222 vw, 2243 vw, 3051 w, 3086 w, 3260 m.
MS (ESI) m/z (%): 779 [M-TfO-] (19), 578 (35), 577 (100), 375 (34), 323 (20), 214 (38).
HRMS (ESI) m/z: [M-TfO-] (C35H29F6N4O6S2) calc.: 779.1427, found: 779.1432. m.p. = 192
- 194 °C (CH2Cl2/MeOH).
SI 11

Helical trication 2
Hexayne 4 (185 mg, 0.20 mmol, 1 eq) and RhCl(PPh3)3 (19 mg, 0.02 mmol, 10 mol%) were
charged into a Schlenk tube, which was then purged with Ar (3x). DMF (8 mL) was then
added. The mixture was stirred at 100 °C for 4 h. After cooling to room temperature, the
mixture was concentrated in vacuo and the resultant residue was mixed with EtOAc and
extracted with H2O (2x). Aqueous layers were collected and water was subsequently removed
on a rotary evaporator. The compound 2 was isolated as a brownish solid in 88 % yield (163
mg, 0.18 mmol).
1H NMR (600 MHz, (CD3)2CO): δ (ppm) = 3.25 (dddt, J = 1.3, 5.0,
15.2, 17.0 Hz, 2H, H-19); 3.36 (ddd, J = 1.8, 4.0, 17.0 Hz, 2H, H-
19); 3.39 (ddd, J = 1.8, 3.0, 15.8 Hz, 2H, H-6); 3.58 (dddt, J = 1.3,
5.2, 14.2, 15.8 Hz, 2H, H-6); 4.23 (dddd, J = 1.0, 3.0, 12.7, 14.2 Hz,
2H, H-7); 4.55 (bddd, J = 4.0, 13.7, 15.2 Hz, 2H, H-18); 5.01 (ddd, J
= 1.8, 5.2, 12.7 Hz, 2H, H-7); 5.18 (bddd, J = 1.8, 5.0, 13.7 Hz, 2H,
H-18); 7.57 (dd, J = 1.0, 7.8 Hz, 2H, H-9); 7.77 (dd, J = 1.0, 7.8 Hz,
2H, H-8); 7.81 (ddd, J = 1.4, 6.1, 7.6 Hz, 2H, H-15); 8.26 (dddd, J =
0.7, 1.6, 7.6, 8.2 Hz, 2H, H-16); 8.59 (ddt, J = 0.6, 1.4, 8.3 Hz, 2H, H-17); 9.07 (ddd, J = 0.7,
1.6, 6.1 Hz, 2H, H-14); 9.67 (bt, J = 0.6 Hz, 1H, H-1). 13C NMR (151 MHz, (CD3)2CO): δ
(ppm) = 27.37 (C-19), 30.50 (C-6), 44.31 (C-7), 56.13 (C-18), 122.96 (C-11), 124.22 (C-4),
124.84 (C-3), 126.74 (C-15), 127.37 (C-17), 131.23 (C-9), 134.42 (C-8), 138.37 (C-1), 139.43
~
(C-10), 139.71 (C-5), 145.81 (C-16), 146.09 (C-12), 147.32 (C-14). IR (KBr): (cm-1) =

420 vw, 518 m, 575 w, 639 s, 696 w, 723 vw, 757 w, 836 vw, 1031 s, 1162 m, 1226 m, 1261
vs, 1276 vs, 1396 vw, 1437 w, 1485 vw, 1510 w, 1543 vw, 1568 w, 3084 w. MS (ESI) m/z
(%): 779 [M-TfO-] (30), 315 [M-2TfO-] (22), 240 (100), 160 [M-3 TfO-] (47). HRMS (ESI)
m/z: [M-TfO-] (C35H29F6N4O6S2) calc.: 779.1427, found: 779.1432. m.p. = 184 - 186 °C
(acetone).
3-Butynyltrifluoromethanesulfonate (9)
CAS: 32264-79-2
Based on a literature procedure.[3]
A solution of starting butynol (760 μL, 10.04 mmol, 1 eq) and pyridine (800 μL, 9.89 mmol,
1 eq) in CH2Cl2 (7 mL) was added to a solution of Tf2O (1.68 mL, 9.99 mmol, 1 eq) in
CH2Cl2 (6 mL) at 0 °C under Ar. The mixture was stirred at 0 °C for 1 h. After warming to
room temperature, the mixture was extracted with H2O (3x). CH2Cl2 layer was dried with
SI 12

Na2SO4. The solvent was removed on a rotary evaporator (300 mbar at 25 °C, not to lose the
rather volatile product 9) and the resultant residue was purified by bulb to bulb distillation
using a Kugelrohr apparatus at 80 °C. Butynyl triflate 9 was isolated as a colorless liquid in
88 % yield (1.76 g, 8.68 mmol).
1H NMR (600 MHz, CDCl3): δ (ppm) = 2.65 (t, J = 2.7 Hz, 1H, H-4), 2.89
(dt, J = 2.7, 6.0 Hz, 2H, H-2), 4.83 (tq, J = 0.6, 6.0 Hz, 2H, H-1). 13C NMR
(151 MHz, CDCl3): δ (ppm) = 20.13 (C-2), 72.57 (C-4), 76.69 (C-1), 78.96
~
(C-3), 119.50 (CF3). IR (CHCl3): (cm-1) = 510 w, 582 w, 615 s, 648 m,

917 m, 962 s, 1145 vs, 1246 s, 1417 vs, 2130 vw, 3309 m.
4) Anion Exchange
Helical trication - iodide 15
A solution of NaI (91 mg, 0.60 mmol, 6.5 eq) in acetone (1 mL) was added to a solution of
trifluoromethanesulfonate 2 (86.3 mg, 0.09 mmol, 1 eq) in acetone (3 mL) under air
atmosphere. The resulting heterogeneous mixture which resulted was stirred at room
temperature for 1 h. The suspension was centrifuged and the liquid was decanted. The solid
residue was washed with acetone (3x). Product 15 was isolated as a yellow solid in 86 % yield
(69 mg, 0.08 mmol).
1H NMR (600 MHz, DMSO-d6): δ (ppm) = 2.95 - 3.03 (m, 2H, H-
15); 3.06 - 3.14 (m, 2H, H-15); 3.19 - 3.24 (m, 4H, H-6); 3.92 - 4.02
(m, 4H, H-7, 14); 4.82 - 4.87 (m, 2H, H-7); 4.91 - 4.96 (m, 2H, H-
14); 7.45 (d, J = 7.7 Hz, 2H, H-9); 7.63 (d, J = 7.7 Hz, 2H, H-8);
7.69 (ddd, J = 1.4, 6.1, 7.6 Hz, 2H, H-17); 8.04 (ddd, J = 1.4, 7.6,
8.3 Hz, 2H, H-18); 8.30 (dd, J = 1.4, 8.3 Hz, 2H, H-19); 8.88 (bdd, J
= 1.4, 6.1 Hz, 2H, H-16); 9.85 (s, 1H, H-1). 13C NMR (151 MHz,
DMSO-d6): δ (ppm) = 26.48 (C-15), 29.51 (C-6), 43.07 (C-7), 54.47
(C-14), 121.72 ( C-11), 123.34 (C-4), 123.59 (C-3), 125.73 (C-17), 126.32 (C-19), 130.06 (C-
9), 133.33 (C-8), 136.90 (C-1), 138.17 (C-10), 138.39 (C-5), 144.43 (C-12), 144.69 (C-18),
~
146.45 (C-16). IR (KBr): (cm-1) = 694 w, 741 w, 787 m, 860 vw, 1347 s, 1434 s, 1455 m,

1506 vs, 1563 s, 1597 m, 1620 s, 2948 m, 3132 w. MS (ESI) m/z (%): 735 [M-I-] (10), 608
(36), 607 (100), 480 (38), 479 (80), 241 (26), 240 (68). HRMS (ESI) m/z: [M-I-]
(C33H29I2N4) calc.: 735.0476, found: 735.0466. m.p. > 330 °C (acetone).
SI 13

Helical trication - chloride 16
The preparation of Dowex resin
Strongly basic anion-exchange resin in Cl- cycle (Dowex® 1x2, Supelco, chloride form, 16-
100 mesh, Cat.No. 13367) was allowed to swell in MeOH overnight. 4 mL of the resin in
MeOH in the initial Cl- cycle was used. For uninterrupted smooth flow of liquid through the
ion-exchanger column, a sinter S0 or a piece of cotton-wool plug at the bottom part of the
column is recommended. All bubbles were removed by mixing the resin with a long needle
or by stoppering the column and turning it gently upside down and back so that all beads of
the resin nicely mixed with MeOH and no bubbles remained. Subsequently, the column was
washed with another portion of MeOH (20 mL).
A solution of trifluoromethanesulfonate 2 (30 mg, 0.03 mmol) in MeOH (2 mL) was run
through a column with Dowex resin in Cl- mode (4 mL). MeOH (20 mL) was used to elute the
trication out of the column. The solvent was then removed on a rotary evaporator. Product 16
was isolated as a brownish solid.
1H NMR (600 MHz, CD3OD): δ (ppm) = 3.06 (bdt, J = 3.6, 15.8 Hz,
2H, H-15); 3.22 (ddd, J = 1.6, 3.8, 17.1 Hz, 2H, H-15); 3.27 - 3.32
(m, 4H, H-6); 4.14 (ddd, J = 7.4, 9.8, 12.6 Hz, 2H, H-7); 4.19 (bdd,
J = 3.6, 13.5 Hz, 2H, H-14); 4.87 (dt, J = 3.4, 12.6 Hz, 2H, H-7);
4.97 (bdd, J = 1.6, 3.8, 13.5 Hz, 2H, H-14); 7.48 (bdd, J = 1.2, 7.7
Hz, 2H, H-9); 7.67 (dt, J = 0.7, 7.7 Hz, 2H, H-8); 7.67 (ddd, J = 1.4,
6.1, 7.6 Hz, 2H, H-17); 8.13 (ddd, J = 0.6, 1.5, 7.6, 8.3 Hz, 2H, H-
18); 8.31 (bdd, J = 1.4, 8.3 Hz, 2H, H-19); 8.86 (ddd, J = 0.6, 1.5,
6.1 Hz, 2H, H-16). 13C NMR (151 MHz, CD3OD): δ (ppm) = 28.03
(C-15), 31.44 (C-6), 44.96 (C-7), 56.58 (C-14), 123.49 (C-11), 124.83 (C-4), 125.64 (C-3),
127.37 (C-17), 127.77 (C-19), 132.04 (C-9), 135.30 (C-8), 140.08 (C-10), 140.33 (C-5),
~
146.49 (C-18), 146.78 (C-12), 147.66 (C-16). IR (KBr): (cm-1) = 694 w, 741 w, 787 m,

860 vw, 1347 s, 1434 s, 1455 m, 1506 vs, 1563 s, 1597 m, 1620 s, 2948 m, 3132 w. MS (ESI)
m/z (%): 551 [M-Cl-] (7), 515 (41), 479 (100). HRMS (ESI) m/z: [M-Cl-] (C33H29Cl2N4)
calc.: 551.1764, found: 551.1764. m.p. = 283 - 285 °C (acetone).
SI 14

5) Capillary Electrophoresis
Capillary electrophoresis (CE) was carried out in a home-made apparatus[4] equipped with a
bare fused silica capillary with outer polyimide coating, total/effective length 400/290 mm,
id/od 50/375 μm (Polymicro Technologies, Phoenix, AR, USA), and UV-absorption detector
operating at a fixed wavelength 206 nm. The new capillary was gradually washed with water,
1 M NaOH, water and background electrolyte, each wash for 10 min. Then, the capillary was
conditioned by a 20 min application of the high voltage to equilibrate the inner capillary
surface with the background electrolyte and to stabilize the electroosmotic flow.
Analyses were performed in the background electrolyte composed of 22 mM sodium, 35 mM
phosphate buffer, pH 2.5, and a chiral selector, 1.5 % sulfated γ-cyclodextrin (highly sulfated
γ-cyclodextrin from Beckman Coulter, Brea, CA, USA, S 808064). The analytes were
dissolved in methanol at ca 5 mM concentration. They were injected into the capillary
hydrodynamically, by pressure 300 – 500 Pa for 3 – 5 s. Analyses were performed at –12 kV
separation voltage (cathode at the injection capillary end), at ambient temperature of 22-25°C.
Chromatography and Electrophoresis Station Clarity (DataApex, Prague, CR) has been
employed for data acquisition and evaluation.
6) UV/Vis Absorption and Fluorescence Spectra
UV/Vis measurements were carried out on a Cary 5000 UV/Vis/NIR spectrophotometer.
Fluorescence measurements were carried out on a Jasco FP-6600 spectrophotometer using
emission measurement mode with 3 nm excitation and 2 nm emission slit widths. Emission
spectra were obtained by exciting at 328 nm. All measurements were carried out in
spectrophotometric grade MeOH (Aldrich, ≥99.9%, CAS: 67-56-1) in cuvettes with 1-cm
path length using 0.052 mM solutions.
7) X-ray Crystallography
Single-crystal X-ray diffraction data for trication 2 (CCDC-955735) were collected on Nonius
KappaCCD diffractometer equipped with Bruker APEX-II CCD detector by
monochromatized MoKα radiation ( λ = 0.71073 Å) at a temperature of 150(2) K. The
structure was solved by direct methods (SHELXS-97)[5] and refined by full-matrix least-
squares based on F with (CRYSTALS).[6] All hydrogen atoms were initially refined with soft
restraints on the bond lengths and angles to regularize their geometry after which the positions
were refined with riding constraints. The non-hydrogen atoms were refined with anisotropic
displacement parameters, except some of the disordered triflate fluorine and oxygen atoms.
Crystal data (0.12 x 0.26 x 0.53 mm)
C33H29N4(CF3SO3)3, monoclinic, space group C2/c, a = 39.389(3) Å, b = 14.2400(12) Å, c =
17.8968(14) Å, β = 114.276(3)°, V = 9150.7(13) Å3, Z = 8, M = 927.78, 27617 reflections
measured, 8976 independent reflections. Final R = 0.097, wR = 0.105, GoF = 1.027 for 4920
reflections with I > 2σ(I) and 633 parameters. The final difference map displayed no peaks of
chemical significance (Δρmax = 1.30, Δρmin -0.78 e.Å-3). Two of the three 3 triflate anions are
disordered. One of them exhibits rotational disorder (site occupation factors being 0.667 and
SI 15

0.333), another one was found to be disordered over two positions (with site occupation
factors 0.5 and 0.5). In consequence, several restraints were used to regularize the thermal
motion of the disordered anions and the atoms with the site occupation factor 0.333 were
refined only isotropically. Furthermore, two partially occupied disordered acetone molecules
were found. These were not included in the refinement and the disordered density was taken
into account using the SQUEEZE procedure (from PLATON).[7] CCDC-955735 contains the
supplementary crystallographic data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
8) References
[1] Amabilino, D. B.; Ashton, P. R.; Reder, A. S.; Spencer, N.; Stoddart, J. F. Angew.
Chem., Int. Ed. 1994, 33, 1286.
[2] Seley, K. L.; Salim, S.; Zhang, L.; O´Daniel, P. I. J. Org. Chem. 2005, 70, 1612.
[3] (a) Beard, C. D.; Baum, K.; Grakauskas, V. J. Org. Chem. 1973, 21, 3673; (b) Severa,
L.; Adriaenssens, L.; Vávra, J.; Šaman, D.; Císařová, I.; Fiedler, P.; Teplý, F.
Tetrahedron 2010, 66, 3537.
[4] Kašička, V.; Prusík, Z.; Sázelová, P.; Brynda, E.; Stejskal, J. Electrophoresis 1999, 20,
2484.
[5] Sheldrick, G. M. Acta Crystallogr., Sect. A: Fundam. Crystallogr. 2008, 64, 112.
[6] Betteridge, P. W.; Carruthers, J. R.; Cooper, R. I.; Prout, K.; Watkin, D. J. J. Appl.
Cryst. 2003, 36, 1487.
[7] Spek, A. L. J. Appl. Cryst. 2003, 36, 7.
SI 16

9) 1H and 13C NMR Spectra
Compound 5 - 1H NMR (acetone-d6)
Compound 5 - 13C NMR (acetone-d6)
SI 17

Compound 7 - 1H NMR (acetone-d6)
Compound 7 - 13C NMR (acetone-d6)
SI 18

Compound 10 - 1H NMR (acetone-d6)
Compound 10 - 13C NMR (acetone-d6)
SI 19

Compound 3 - 1H NMR (acetone-d6)
Compound 3 - 13C NMR (acetone-d6)
SI 20

Compound 1 - 1H NMR (acetone-d6)
Compound 1 - 13C NMR (acetone-d6)
SI 21

Compound 1 - H,C-HSQC (acetone-d6)
SI 22

Compound 14 - 1H NMR (acetone-d6)
Compound 14 - 13C NMR (acetone-d6)
SI 23

Compound 12 - 1H NMR (acetone-d6)
Compound 12 - 13C NMR (acetone-d6)
SI 24

Compound 13 - 1H NMR (acetone-d6)
Compound 13 - 13C NMR (acetone-d6)
SI 25

Compound 4 - 1H NMR (acetone-d6)
Compound 4 - 13C NMR (acetone-d6)
SI 26

Compound 2 - 1H NMR (acetone-d6)
SI 27

Compound 2 - 13C NMR (acetone-d6)
SI 28

Compund 15 - 1H NMR (DMSO-d6)
Compound 15 - 13C NMR (DMSO-d6)
SI 29