Supporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2003

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1 Supporting Informtion for Angew. Chem. Int. Ed. Z52047 Wiley-VCH Weinheim, Germny

2 The Verstile Synthesis nd Self-ssembly of Str-type Hexbenzocoronenes Jishn Wu, Mrk D. Wtson, Klus Müllen Mx-Plnck Institute for Polymer Reserch, Ackermnnweg 10, D-55128, Minz, Germny ew ddress: University of Kentucky, Dept. Chemistry, Lexington, Kentucky (USA). E-mil: Fx:

3 1. MALDI-MS of compound 2, 11-c. (TCQ s mtrix) ntens. 2 x104 0,8 11 Cl. m/z= ,6 Cl. m/z= ,4 0, m/z 0, m/z Intens. x10 4 0,8 11b ntens. x10 4 1,25 1,00 11c Cl. m/z= Cl. m/z= ,6 0, ,75 0, , ,25 0, m/z 0, m/z 2. MALDI-MS of compound 12-b (TCQ s mtrix) Cl. m/z= b Cl. m/z= m/z m/z 3. 1 H MR spectr (500MHz) of 11-c (413K in d4-tetrchloroethne), 12 (d4-1,2- dichlorobenzene, 443K, only monomer exists), 12b (413K in d4-tetrchloroethne) nd 15 (413K in d4-tetrchloroethne). 2

4 () Hb Hc b c (b) O O O O Hb HcHd OC 12 H He 25 O,b,c d,e

5 (c) O O O O O O O O O O O O Hb Hc Hd O O O O O O bc d 9.0 (d) Hb Hc b c

6 (e) Hb Hc Hd d b c (f) Hb Hc Hd He Hf Hg g f c,d b e 9.0 5

7 4. Synthesis of compound 14. The synthetic route to compound 14 is outlined s shown below. Selective gihr coupling rection between 1-bromo-4-iodobenzene nd triisopropylsilylcetylene gve compound 16, which ws followed by plldium-ctlyzed Buchwld coupling rection with di(4-octylphenyl)mine (commercilly vilble) to provide compound 17. Compound 14 ws then fcilely obtined by removing the triisopropylsilyl group with tetrbutylmmonium fluoride (TBAF) in THF. I Br + Si Pd(2+)-CuI Et 3, r.t. Si Br + 16 H Pd2(db)3-P(tert-Bu)3 Toluene, r.t. Si TBAF THF, r.t Synthesis of compound 16: 8g 1-bromo-4-iodobenzene (28.28mmol), 991 mg Pd(PPh 3 ) 2 Cl 2, mg CuI nd 185 mg PPh 3 were dissolved in 180 ml triethylmine nd 60 ml toluene. The mixture ws degssed by bubbling rgon for 15 min nd then 6.2 g triisopropylsilycetylene ws dded. After stirring overnight t room temperture, the mixture ws poured into wter nd extrcted by dichloromethne. The orgnic lyer ws wshed by wter three times nd dried over MgSO 4. The solvent ws removed under vcuum nd the residue ws purified by column chromtogrphy (xne, silic gel) to provide 7.8 g colorless oil (81.7%). 1 H MR (CD 2 Cl 2,250 MHz): d ppm (d, J=8.5 Hz, 2H), (J=8.2 Hz, 2H), (overlpped, 21 H); FD-MS (8 kv): m/z= Synthesis of compound 17: 2.38 g compound 16, 2.5 g di(4-octylphenyl)mine, 58.6 mg Pd 2 (db) 3, 20.7 mg tri-tertbutylphosphorous, mg sodium tert-butoxide nd 12 ml wter-free toluene were mixed together in 25 ml Schlenk tube in glove box. The mixture ws stirred t room temperture 6

8 for 3.5 hours nd quenched by dding sturted mmonium chloride solution. After extrction with diethyl ether, wshing nd column chromtogrphy (PE, Al 2 O 3 ) work-up, 2.3g 17 ws obtined (50.2%). FD-MS (8kV): m/z=650.3, 1 H MR (CD 2 Cl 2, 250 MHz): ): d ppm (d, J=8.5 Hz, 4H), (d, J=8.8 Hz, 2H), 6,981 (d, J=8.8 Hz, 4H), (d, J=8.8 Hz, 2H), (m, 4H), (m, 12H), (m, 21H), (m, 18H). Synthesis of compound 14: A solution of 1.2 g compound 17 in 10 ml THF ws degssed by bubbling rgon nd then 873 mg tetrbutylmmonium fluorid trihydrte ws dded. The mixture ws stirred t room temperture for 30 min nd ws quenched by dding sturted mmonium chloride solution. The mixture ws extrcted by diethyl ether. The orgnic lyer ws wshed by wter three times nd dried over MgSO 4. Removing the solvent provided compound 786 mg compound 14 (86%). o further purifiction is needed considering the quntittive conversion nd lso to void possible oxidtion of the monosubstituted cetylene. FD-MS (8kV): m/z= 493.9; 1 H MR (CD 2 Cl 2, 250 MHz): ): d ppm (d, J=8.5 Hz, 4H), (d, J=8.8 Hz, 2H), 6,981 (d, J=8.8 Hz, 4H), (d, J=8.8 Hz, 2H), 33 (s, 1H), (m, 4H), (m, 12H), (m, 18H). 5. Synthesis of compound 15---A representtive gihr-sonogshir coupling rection between monoethynylenes nd building block 2. To frme-dried 25 ml Schlenk flsk ws dded mg compound 2 (0.173 mmol), 17.5 mg Pd(PPh 3 ) 4 (2.5 mol % per I), 5.7 mg of copper iodide ( mol % per I), nd 10 ml piperidine. The mixture ws degssed by bubbling rgon for 15 min, then 592 mg 14 (76 mmol) ws dded. The solution ws heted to 52 C overnight, cooled to RT, nd 20 ml methnol ws dded. The yellow precipitte ws collected, followed by column chromtogrphy (Al 2 O 3, PE/DCM=7/3) to give 253 mg pure compound 15 (64.4%). 1 H MR (500 MHz, C 2 D 2 Cl 4, 413 K): d ppm (s, 12H), (m, 24H), (m, 12H), (d, J=6.4 Hz, 24H), 21(d, J=6.4 Hz, 24H), 6.976(m, 12H). MALDI-MS (TCQ s mtrix): m/z= Synthesis of compound A generl procedure for six-fold Diels-Alder cycloddition. 57 mg compound 11 nd 493 mg tetrphenylcyclopentdienone were dissolved in 2 ml 7

9 diphenyl ether. The mixture ws heted to 250 C for 18 h under rgon nd cooled down to room temperture. Then 20 ml methnol ws dded nd the precipitte ws collected nd purified by column chromtogrphy (PE/DCM=3:2, silic gel) to provide 101 mg pure product (88.6%) s yellow powder. MALDI-MS (TCQ s mtrix): m/z= H MR spectrum in C 6 Cl 2 D 4 t 443K (t this temperture, only monomer exist) is shown s bove. 8