# Luminescence Tuning of Fluorinated Bistolanes via Electronic or Aggregated-Structure Control
## 2 Materials and Methods
### Preparation of \(Cf_{3}\)-Substituted Bistolane **1 aC**  
In a 50 mL two-necked round-bottomed flask was placed 4-[2-(4-methoxyphenyl)ethyn-1-yl]phenylacetylene (**3a**, 0.46 g, 2.0 mmol) in THF (30 mL). The solution was cooled to 0 \({}^{\circ}\)C and then \(n\)-BuLi (1.6 mol L\({}^{-1}\) hexane solution, 1.3 mL, 2.0 mmol) was added. The mixture was stirred at 0 \({}^{\circ}\)C for 0.5 h. Then, perfluoroluene (**C**, 0.42 mL, 3.0 mmol) was added dropwise at 0 \({}^{\circ}\)C and the resultant solution was continuously stirred at room temperature overnight. The reaction mixture was poured into saturated aqueous NH\({}_{4}\)Cl solution (40 mL). The crude product was extracted using AcOEt (40 mL, three times) and washed with brine (40 mL, once). The organic layer was dried over anhydrous Na\({}_{2}\)SO\({}_{4}\), filtered, and concentrated using a rotary evaporator. The resultant crude product was purified by silica-gel column chromatography using hexane/AcOEt (20:1, \(\
u\)/\(\
u\)) as an eluent, yielding coupling product **1 aC** (0.32 g, 0.72 mmol) in 36% yield as a white solid. This product was recrystallized by slow evaporation from CH\({}_{2}\)Cl\({}_{2}\)/MeOH (1:1, \(\
u\)/\(\
u\)) to obtain **1 aC** in crystalline form.  
4.1 1-Trifluoromethyl-2,3,5,6-tetrafluoro-4-[2-[4-[2-(4-methoxyphenyl)]ethyn-1-yl]phenyl]ethyn-1-yl]benzene (**1 aC**)  
Yield: 36% (white solid); mp: 168 \({}^{\circ}\)C determined by DSC; \({}^{1}\)H NMR (CDCl\({}_{3}\)): \(\delta\) 3.84 (s, 3H), 6.88-6.91 (m, 2H), 7.47-7.50 (m, 6H); \({}^{13}\)C NMR (CDCl\({}_{3}\)): \(\delta\) 55.5, 74.9 (t, \(J\) = 3.7 Hz), 87.7, 92.8, 104.7, 108.8-109.3 (m), 109.7-109.8 (m, 1C), 114.3, 114.9, 120.7 (q, \(J\) = 273.6 Hz), 120.3, 125.9, 131.7, 132.2, 133.4, 142.9-145.7 (m), 145.8-148.3 (m), 160.2; \({}^{19}\)F NMR (CDCl\({}_{3}\)): \(\delta\) - 56.67 (t, \(J\) = 23.2 Hz, 3F), \(-\)135.09 (dddd, \(J\) = 18.1, 18.1, 5.7 Hz, 2F), \(-\)141.27 (m, 2F); IR (KBr): \(\
u\) 2360, 2210, 1660, 1643, 1595, 1493, 1404, 1345 cm\({}^{-1}\); HRMS (FAB\({}^{+}\)) \(m\)/\(\gtrsim\) [M]\({}^{+}\) calcd for C\({}_{24}\)H\({}_{11}\)O\({}_{7}\): 448.0698; found: 448.0699.  
4.2 1-Trifluoromethyl-2,3,5,6-tetrafluoro-4-[2-[4-[2-(4-hexyloxyphenyl)ethyn-1-yl]phenyl]ethyn-1-yl]benzene (**1 bc**)  
Yield: 32% (white solid); mp: 133 \({}^{\circ}\)C determined by DSC; \({}^{1}\)H NMR (CDCl\({}_{3}\)): \(\delta\) 0.91 (t, \(J\) = 7.0 Hz, 3H), 1.33-1.37 (m, 4H), 1.43-1.50 (m, 2H), 1.76-1.83 (m, 2H), 3.98 (t, \(J\) = 6.6 Hz, 2H), 6.87-6.89 (m, 2H), 7.45-7.48 (m, 2H), 7.52-7.59 (m, 4H); \({}^{13}\)C NMR (CDCl\({}_{3}\)): \(\delta\) 14.1, 22.7, 25.8, 29.3, 31.7, 68.3, 74.9 (t, \(J\) = 7.2 Hz), 87.6, 93.0, 104.7 (t, \(J\) = 4.2 Hz), 108.9-109.2 (m, 1C), 114.6, 114.8, 120.7 (q, \(J\) = 273.6 Hz), 120.2, 125.9, 131.6, 132.2, 133.3, 143.0-145.6 (m, 1C), 145.8-148.3 (m, 1C), 159.8 (one sp-carbon was overlapped with another alkyne carbon); \({}^{19}\)F NMR (CDCl\({}_{3}\)): \(\delta\) - 56.77 (t, \(J\) = 23.2 Hz, 3F), \(-\)135.13 (ddd, \(J\) = 18.2, 18.2, 5.9 Hz, 2F), \(-\)141.39 (m, 2F); IR (KBr): \(\
u\) 2957, 2894, 2360, 2211, 1659, 1606, 1594 cm\({}^{-1}\); HRMS (FAB\({}^{+}\)) \(m\)/\(\gtrsim\) [M]\({}^{+}\) calcd for C\({}_{29}\)H\({}_{21}\)O\({}_{7}\): 518.1481; found: 518.1484.