# Luminescence Tuning of Fluorinated Bistolanes via Electronic or Aggregated-Structure Control
## 2 Materials and Methods
### Preparation of AcO-substituted Bistolane **1 aB**  
In a 50 mL two-necked round-bottomed flask were placed Cl\({}_{2}\)Pd(PPh\({}_{3}\))\({}_{2}\) (0.051 g, 0.050 mmol), PTh\({}_{3}\) (0.015 g, 0.050 mmol), CuI (0.031 g, 0.10 mmol), 4-[2-(4-methoxyphenyl)ethyln-1-yl]phenylacetylene (**3a**, 0.24 g, 1.0 mmol), and 4-acetoxy-2,3,5,6-tetrafluoroidobenzene (**B**, 0.41 g, 1.2 mmol) in Et\({}_{3}\)N (10 mL) and THF (5 mL). The mixture was stirred at reflux temperature overnight. The precipitate formed in the reaction mixture was separated by atmospheric filtration and the filtrate was poured into saturated aqueous NH\({}_{4}\)Cl solution (20 mL). The crude product was extracted using AcOEt (20 mL, three times) and washed with brine (20 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, providing coupling product **1 aB** (0.21 g, 0.48 mmol) in 48% yield as a white solid. This product was recrystallized by slow evaporation from CH\({}_{2}\)Cl\({}_{2}\)/MeOH (1:1, _v/v_) to obtain **1 aB** in crystalline form.  
3.1 1-Acetoxy-2,3,5,6-tetrafluoro-4-[2-[4-[2-(4-methoxyphenyl)ethyln-1-yl]phenyl]]]]]]]]]]=-1-yl]benzene (**1 aB**)  
Yield: 48% (white solid); mp: 159 \({}^{\circ}\)C determined by differential scanning calorimetry (DSC); 1H NMR (CDCl\({}_{3}\)): 8 2.42 (s, 3H), 3.84 (s, 3H), 6.88-6.91 (m, 2H), 7.47-7.57 (m, 6H); 1\({}^{3}\)C NMR (CDCl\({}_{3}\)): 8 20.0, 55.4, 75.3 (t, \(J\) = 4.0 Hz), 87.8, 92.3, 101.6 (t, \(J\) = 3.8 Hz), 102.3 (t, \(J\) = 18.0 Hz), 114.0, 114.9, 121.0, 125.1, 129.3 (t, \(J\) = 14.7, 2.9 Hz), 131.6, 132.0, 133.3, 139.5-142.2 (m, \(C_{\rm Ar}\)-F, 1C), 145.6-148.4 (m, \(C_{\rm Ar}\)-F, 1C), 160.1, 166.6; 1\({}^{9}\)F NMR (CDC\({}_{3}\)): \(\delta\) - 137.34 (dd, \(J\) = 23.9, 9.9 Hz, 2F), -153.66 (dd, \(J\) = 23.9, 9.9 Hz, 2F); IR (KBr): \(v\) 2362, 2210, 1792, 1596, 1491, 1394, 1315 cm\({}^{-1}\); HRMS (FAB\({}^{+}\)) _m/z_ [M]\({}^{+}\) calcd for C\({}_{25}\)H\({}_{14}\)O\({}_{3}\)F\({}_{4}\): 438.0879; found: 438.0881.  
3.2 1-Acetoxy-2,3,5,6-tetrafluoro-4-[2-[4-[2-(4-hexyloxyphenyl)]ethyn-1-yl]phenyl]ethyn-1-yl]benzene (**1b**B)  
Yield: 54% (white solid); mp: 143 \({}^{\circ}\)C determined by DSC; \({}^{1}\)H NMR (CDCl\({}_{3}\)): \(\delta\) 0.91 (t, \(J\) = 7.0 Hz, 3H), 1.32-1.37 (m, 4H), 1.43-1.50 (m, 2H), 1.76-1.83 (m, 2H), 3.42 (s, 3H), 3.98 (t, \(J\) = 6.6 Hz, 2H), 6.87-6.89 (m, 2H), 7.45-7.48 (m, 2H), 7.50-7.56 (m, 4H); \({}^{13}\)C NMR (CDCl\({}_{3}\)): \(\delta\) 14.2, 20.1, 22.7, 25.8, 29.3, 31.7, 68.3, 75.3 (t, \(J\) = 4.3 Hz), 87.7, 92.5, 101.6 (t, \(J\) = 4.3 Hz), 102.4 (t, \(J\) = 18.1 Hz), 114.8, 121.0, 125.2, 129.3 (tt, \(J\) = 17.6, 2.9 Hz), 131.6, 132.0, 133.3, 139.5-142.0 (m, \(C_{\rm Ar}\)-F, 1C), 145.7-148.3 (m, \(C_{\rm Ar}\)-F, 1C), 159.7, 166.6 (one sp-carbon was overlapped with another alkyne carbon); \({}^{19}\)F NMR (CDCl\({}_{3}\)): \(\delta\) = 137.90 (dd, \(J\) = 23.1, 9.8 Hz, 2F), \(-\)154.22 (dd, \(J\) = 23.1, 9.8 Hz, 2F); IR (KBr): \(\
u\) 2962, 2860, 2367, 2208, 1795, 1597, 1495, 1405 cm\({}^{-1}\); HRMS (FAB\({}^{+}\)) \(m\)/\(\gtrsim\) [M]\({}^{+}\) calcd for C\({}_{30}\)H\({}_{24}\)O\({}_{3}\)F\({}_{4}\): 508.1662; found: 508.1655.