Interesting compound, Spoked-wheel macrocycles

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• Chemical Formula: C₇₇₄H₉₉₆N₁₈O₃₆Si₁₂
• Molecular Weight: 11465.32
• Elemental Analysis: C, 81.08; H, 8.76; N, 2.20; O, 5.02; Si, 2.94

 4-({2-[4-(2-{9-[4-(4-{2-[2,5-Bis(octyloxy)-4-(2-{4-[pentakis({4-[2-(4-{2-[4-(4-{2,7-bis[2-(4-{2-[(3-cyanopropyl)bis(propan-2-yl)silyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]-9H-carbazol-9-yl}phenyl)phenyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]phenyl})phenyl]phenyl}ethynyl)phenyl]ethynyl}phenyl)phenyl]-7-[2-(4-{2-[(3-cyanopropyl)bis(propan-2-yl)silyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]-9H-carbazol-2-yl}ethynyl)-2,5-bis(octyloxy)phenyl]ethynyl}bis(propan-2-yl)silyl)butanenitrile

Compound 7

From Fluctuating exciton localization in giant π-conjugated spoked-wheel macrocycles

• A. Vikas Aggarwal,
• Alexander Thiessen,
• Alissa Idelson,
• Daniel Kalle,
• Dominik Würsch,
• Thomas Stangl,
• Florian Steiner,
• Stefan-S. Jester,
• Jan Vogelsang,
• Sigurd Höger
• & John M. Lupton

Nature Chemistry5,964–970(2013)

doi:10.1038/nchem.1758

Supplementary Information

 

C774H996N18O36Si12
Name compound: 4-({2-[4-(2-{9-[4-(4-{2-[2,5-Bis(octyloxy)-4-(2-{4-[pentakis({4-[2-(4-{2-[4-(4-{2,7-bis[2-(4-{2-[(3-cyanopropyl)bis(propan-2-yl)silyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]-9H-carbazol-9-yl}phenyl)phenyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]phenyl})phenyl]phenyl}ethynyl)phenyl]ethynyl}phenyl)phenyl]-7-[2-(4-{2-[(3-cyanopropyl)bis(propan-2-yl)silyl]ethynyl}-2,5-bis(octyloxy)phenyl)ethynyl]-9H-carbazol-2-yl}ethynyl)-2,5-bis(octyloxy)phenyl]ethynyl}bis(propan-2-yl)silyl)butanenitrile.

https://www.instagram.com/p/BBMfA4bBkvZY9QhsJV6ff6khLjUE6F9MqBqRu40/

• Synthetic Procedure: See article for the definitive version of this procedure and for full experimental details.6 (19.0 mg, 14.7 µmol), CuI (3.4 mg, 17.7 µmol), Pd₂dba₃(4.0 mg, 4.4 µmol), and tri(t‑butyl)phosphine (6.0 mg, 29.5 µmol) were mixed in a microwave tube and sealed with a septum. In parallel, a solution of 5 (241.7 mg, 132.6 µmol) in piperidine (2 mL) was purged with argon for 1 h. Then the latter was transferred to the microwave tube and the mixture was heated at 120 °C for 16 min in a microwave instrument (max. power: 300 W). After cooling to r.t., the tube was opened and the reaction mixture was diluted with MTBE. The organic phase was washed with aq. H₂SO₄ (10 %) and brine. It was dried over MgSO₄ and the solvent was removed under reduced pressure. The residue was purified by column chromatography (CH:DCM = 65:35 ‑ 68:32), and 7 (126 mg, 10.9 µmol, 74 %) was obtained as a yellow solid. ¹H NMR (500 MHz, CDCl₃, 298 K) δ [ppm] = 8.09 (d, ³J_H,H = 8.2 Hz, 12 H), 7.87 (d, ³J_H,H = 8.5 Hz, 12 H), 7.76 – 7.60 (m, 48 H), 7.55 – 7.46 (m, 12 H), 7.16 (d, ³J_H,H = 8.0 Hz, 12 H), 7.03 (s, 6 H), 7.02 (s, 6 H), 6.96 (s, 12 H), 6.93 (s, 12 H), 6.86 (d, ³J_H,H = 8.1 Hz, 12 H), 4.10 – 3.99 (m, 48 H), 3.99 – 3.90 (m, 24 H), 2.42 (t, ³J_H,H = 7.0 Hz, 24 H), 1.95 – 1.72 (m, 96 H), 1.62 – 1.16 (m, 360 H), 1.15 – 0.97 (m, 168 H), 0.97 – 0.76 (m, 132 H); ¹H NMR (500 MHz, CD₂Cl₂, 298 K) δ [ppm] = 8.14 (d, ³J_H,H = 8.1 Hz, 12 H), 7.92 (d, ³J_H,H = 8.5 Hz, 12 H), 7.79 – 7.66 (m, 36 H), 7.64 (s, 12 H), 7.54 – 7.44 (m, 12 H), 7.20 (d, ³J_H,H = 8.2 Hz, 12 H), 7.05 (s, 6 H), 7.02 (s, 6 H), 6.99 (s, 12 H), 6.97 – 6.93 (m, 24 H), 4.08 – 3.98 (m, 48 H), 3.98 – 3.92 (m, 24 H), 2.41 (t, ³J_H,H = 7.0 Hz, 24 H), 1.96 – 1.71 (m, 96 H), 1.65 – 1.17 (m, 360 H), 1.17 – 0.99 (m, 168 H), 0.99 – 0.76 (m, 132 H); ¹³C NMR (126 MHz, CDCl₃, 298 K) δ [ppm] = 154.78, 154.06, 153.94, 153.79, 141.60, 140.49, 140.41, 140.10, 136.79, 132.63, 131.73, 130.90, 128.94, 127.99, 127.36, 124.58, 123.55, 123.50, 121.54, 121.26, 120.86, 120.21, 118.04, 117.40, 117.28, 116.51, 114.96, 114.65, 114.07, 113.58, 113.47, 104.31, 96.51, 95.56, 94.91, 87.61, 86.62, 70.16, 70.04, 70.00, 69.56, 32.27, 32.25, 32.24, 32.18, 29.82, 29.79, 29.75, 29.73, 29.71, 29.68, 26.52, 26.42, 26.40, 23.14, 23.13, 23.09, 23.08, 21.70, 21.17, 18.65, 18.41, 14.63, 14.57, 14.52, 14.50, 12.20, 10.04; ¹³C NMR (126 MHz, CD₂Cl₂, 298 K) δ [ppm] = 154.88, 154.20, 154.11, 153.93, 141.87, 140.89, 140.63, 140.50, 140.40, 136.88, 132.68, 132.04, 130.83, 129.11, 128.15, 127.61, 124.49, 123.69, 123.50, 121.66, 121.44, 121.10, 120.32, 117.99, 117.47, 117.28, 116.70, 114.90, 114.62, 114.20, 113.84, 113.62, 104.31, 96.45, 95.91, 95.35, 94.94, 87.71, 86.85, 86.80, 70.22, 70.14, 69.82, 32.44, 32.35, 29.97, 29.93, 29.90, 29.88, 29.83, 29.83, 26.69, 26.67, 26.58, 26.54, 23.31, 23.29, 23.25, 23.24, 21.89, 21.22, 18.56, 18.32, 14.57, 14.50, 14.45, 14.43, 12.35, 10.14;MS (MALDI-TOF, DCTB) (calcd. for C₇₇₄H₉₉₆N₁₈O₃₆Si₁₂ monoisotopic: 11455.39, distr. max.: 11465.32): m/z11965.9 [M+2*DCTB]⁺, 11716.6 [M+DCTB]⁺, 11465.3 [M]⁺, 5856.8 [M+DCTB]²⁺, 5733.5 [M]²⁺; GPC (in THF vs. PS): M_p = 11580 g mol^-1.

Soheil Zabihi
 http://www.nature.com/nchem/journal/v5/n11/compound/nchem.1758_comp7.html
http://www.nature.com/nchem/journal/v5/n11/extref/nchem.1758-s1.pdf
http://www.nature.com/nchem/journal/v5/n11/extref/nchem.1758-s1.pdf

Affiliations

1. Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany

   • A. Vikas Aggarwal,
   • Alissa Idelson,
   • Daniel Kalle,
   • Stefan-S. Jester &
   • Sigurd Höger

2. Department of Physics and Astronomy, University of Utah, Salt Lake City, Utah 84112, USA

   • Alexander Thiessen &
   • John M. Lupton

3. Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstrasse 31, D-93040 Regensburg, Germany

   • Dominik Würsch,
   • Thomas Stangl,
   • Florian Steiner,
   • Jan Vogelsang &
   • John M. Lupton

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SMILES: CCCCCCCCOC(C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C1)=C1C#CC2=CC3=C(C=C2)C4=C(C=C(C#CC5=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C5)C=C4)N3C(C=C6)=CC=C6C(C=C7)=CC=C7C#CC(C=C8OCCCCCCCC)=C(OCCCCCCCC)C=C8C#CC(C=C9)=CC=C9C%10=C(C%11=CC=C(C#CC%12=C(OCCCCCCCC)C=C(C#CC%13=CC=C(C%14=CC=C(N%15C(C=C(C#CC%16=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%16OCCCCCCCC)C=C%17)=C%17C%18=C%15C=C(C#CC%19=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%19OCCCCCCCC)C=C%18)C=C%14)C=C%13)C(OCCCCCCCC)=C%12)C=C%11)C(C%20=CC=C(C#CC%21=C(OCCCCCCCC)C=C(C#CC%22=CC=C(C%23=CC=C(N%24C(C=C(C#CC%25=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%25)C=C%26)=C%26C%27=C%24C=C(C#CC%28=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%28)C=C%27)C=C%23)C=C%22)C(OCCCCCCCC)=C%21)C=C%20)=C(C%29=CC=C(C#CC%30=CC(OCCCCCCCC)=C(C#CC%31=CC=C(C%32=CC=C(N%33C(C=C(C#CC%34=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%34)C=C%35)=C%35C%36=C%33C=C(C#CC%37=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%37)C=C%36)C=C%32)C=C%31)C=C%30OCCCCCCCC)C=C%29)C(C%38=CC=C(C#CC%39=C(OCCCCCCCC)C=C(C#CC%40=CC=C(C%41=CC=C(N%42C(C=C(C#CC%43=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%43OCCCCCCCC)C=C%44)=C%44C%45=C%42C=C(C#CC%46=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%46OCCCCCCCC)C=C%45)C=C%41)C=C%40)C(OCCCCCCCC)=C%39)C=C%38)=C%10C%47=CC=C(C#CC%48=C(OCCCCCCCC)C=C(C#CC%49=CC=C(C%50=CC=C(N%51C(C=C(C#CC%52=C(OCCCCCCCC)C=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C(OCCCCCCCC)=C%52)C=C%53)=C%53C%54=C%51C=C(C#CC%55=CC(OCCCCCCCC)=C(C#C[Si](C(C)C)(C(C)C)CCCC#N)C=C%55OCCCCCCCC)C=C%54)C=C%50)C=C%49)C(OCCCCCCCC)=C%48)C=C%47