# Luminescence Tuning of Fluorinated Bistolanes via Electronic or Aggregated-Structure Control
## 2 Materials and Methods
### Preparation of CN-Substituted Bistolane **1 aC**  
In a 50 mL two-necked round-bottomed flask was placed 4-[2-(4-methoxyphenyl)ethyn-1-yl]phenylacetylene (**3a**, 0.47 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, perfluoroobenzonitrile (**D**, 0.30 mL,2.4 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, _v/v_) as an eluent, yielding coupling product **1 aD** (0.26 g, 0.64 mmol) in 32% yield as a yellow solid. This product was recrystallized by slow evaporation from CH\({}_{2}\)Cl\({}_{2}\)/MeOH (1:1, _v/v_) to obtain **1 aD** in crystalline form.  
.5.1 1-Cyano-2,3,5,6-tetrafluoro-4-[2-[4-[2-(4-methoxyphenyl)]]]phenyl/ethyln-1-yl]benzene (**1 aD**)  
Yield: 32% (yellow solid); mp: 195 \({}^{\circ}\)C determined by DSC; \({}^{1}\)H NMR (CDCl\({}_{3}\)): \(\delta\) 3.84 (s, 3H), 6.87-6.92 (m, 2H), 7.47-7.50 (m, 6H), 7.52-7.61 (m, 4H); \({}^{13}\)C NMR (CDCl\({}_{3}\)): \(\delta\) 55.5, 75.2, 87.7, 93.1, 93.3, 107.1 (dt, \(J\) = 84.9, 4.9 Hz), 110.5 (d, \(J\) = 2.3 Hz), 111.2 (t, \(J\) = 2.8 Hz), 114.3, 114.9, 120.0, 126.3, 131.7, 132.3, 133.4, 145.3-146.0 (m), 147.8-148.7 (m), 160.2, \({}^{19}\)F NMR (CDCl\({}_{3}\)): \(\delta\) \(-\) 133.19 (ddd, \(J\) = 18.0, 18.0, 6.7 Hz, 2F), \(-\)133.90 (ddd, \(J\) = 18.0, 17.9, 6.1 Hz, 2F); IR (KBr): \(\
u\) 2351, 2207, 1643, 1595, 1487, 1478 cm\({}^{-1}\); HRMS (FAB\({}^{+}\)) _m/z_ [M]\({}^{+}\) calcd for C\({}_{24}\)H\({}_{11}\)NOF\({}_{4}\): 405.0777; found: 405.0780.  
5.2 1-Cyano-2,3,5,6-tetrafluoro-4-[2-[4-[2-(4-hexyloxyphenyl)]]]phenyl/ethyln-1-yl]benzene (**1 bD**)  
Yield: 17% (yellow solid); mp: 154 \({}^{\circ}\)C determined by DSC; \({}^{1}\)H NMR (CDCl\({}_{3}\)): \(\delta\) 0.91 (t, \(J\) = 6.9 Hz, 3H), 1.32-1.37 (m, 4H), 1.44-1.48 (m, 2H), 1.79 (quin, \(J\) = 7.0 Hz, 2H), 3.98 (t, \(J\) = 6.6 Hz, 2H), 6.87-6.90 (m, 2H), 7.45-7.48 (m, 2H), 7.52-7.59 (m, 4H); \({}^{13}\)C NMR (CDCl\({}_{3}\)): \(\delta\) 14.2, 22.7, 25.8, 29.3, 31.7, 68.3, 75.5, 87.9, 93.3 (m), 93.3, 106.6-108.3 (m), 110.0, 111.3 (m), 114.6, 114.8, 119.9, 126.3, 131.7, 132.3, 133.4, 143.5-143.8 (m), 144.9-145.1 (m), 159.91; \({}^{19}\)F NMR (CDCl\({}_{3}\)): \(\delta\) \(-\) 133.24 (ddd, \(J\) = 19.5, 17.8, 6.3 Hz, 2F), \(-\)133.94 (ddd, \(J\) = 19.5, 17.8, 6.3 Hz, 2F); IR (KBr): \(\
u\) 2944, 2872, 2210, 1645, 1606, 1596, 1520, 1474, 1416 cm\({}^{-1}\); HRMS (FAB\({}^{+}\)) _m/z_ [M]\({}^{+}\) calcd for C\({}_{29}\)H\({}_{21}\)NOF\({}_{4}\): 475.1559; found: 475.1549.