## 2 Materials and Methods
### Synthesis of Objects
#### 2.3.2 General Synthesis of Organic Salts of POMs  
Organic salts of POMs were synthesized by mixing the corresponding heteropolyacid with x equivalent of Butyl methyl imidazolium chloride, or 1-butyl pyridinium bromide in water. The salt formed was filtered then dried after washing with water. **(BmIm)\({}_{3}\)PMo\({}_{12}\)O\({}_{40}\)**: \({}^{1}\)H\({}_{3}\)PMo\({}_{12}\)O\({}_{40}\):21H\({}_{2}\)O (1 g 0.45 mmol) was mixed with 1-butyl-3-methyl imidazolium chloride (0.29 g, 1.3 mmol) in 10 mL water at room temperature for 4 h. The light green salt formed was filtered and dried under vacuum. Yield: 94%. (C\({}_{8}\)H\({}_{15}\)N\({}_{2}\))\({}_{3}\)PMo\({}_{12}\)O\({}_{40}\) Anal. Calc: C, 12.87; H, 2.03; N,3.75. Found: C, 13.03; H, 1.56; N, 3.87. IR (ATR, \(\
u\)(cm\({}^{-1}\))): 3150-2850 (CH), 1563 (C=C), 1460 (C-N), 1060 (P-O), 953 (Mo=O), 780(Mo-O-Mo). \({}^{1}\)H NMR (400 MHz, DMSO-d\({}_{6}\)) \(\delta\) = 9.1 (s, 1H, NCHN), 7.78 (s, 1H, NCH), 7.72 (s, 1H, NCH), 4.21 (t, \(J\) = 7.1 Hz, 2H, NCH\({}_{2}\)), 3.89 (s, 3H, NCH\({}_{3}\)), 1.81(m, 2H, CH\({}_{2}\)), 1.25 (dq, \(J\) = 14.7, 7.3 Hz, 2H, CH\({}_{2}\)), 0.91 (t, \(J\) = 7.4 Hz, 3H, but-CH\({}_{3}\)). \({}^{13}\)C[\({}^{1}\)H] NMR (101 MHz, DMSO-d\({}_{6}\)) \(\delta\) = 136.94, 124.12, 122.75, 48.99, 36.19, 31.86, 19.25, 13.76. \({}^{31}\)P[\({}^{1}\)H] NMR (162 MHz, DMSO-d\({}_{6}\)) \(\delta\) = \(-\)1.36 (minor), \(-\)4.11 (major). **(Bm1m)4 PMo\({}_{11}\)VO\({}_{40}\)**: H\({}_{4}\)PMo\({}_{11}\)VO\({}_{40}\).28H\({}_{2}\)O (1 g, 0.43 mmol) was mixed with 1-butyl-3-methyl imidazolium chloride (0.38 g, 1.7 mmol) in 10 mL water at room temperature for 4 h. The yellow salt formed was filtered and dried under vacuum. Yield: 94%, (C\({}_{8}\)H\({}_{15}\)N\({}_{2}\))\({}_{4}\)PMo\({}_{11}\)VO\({}_{40}\) Anal. Calc: C, 16.47; H, 2.59; N,4.8. Found: C, 16.95; H, 1.97, N, 4.78. IR (ATR, v(cm\({}^{-1}\))): 3150-2850 (CH), 1568 (C=C), 1466 (C-N), 1063 (P-O), 953 (Mo=O), 740-880 (M-O-M). \({}^{1}\)H NMR (400 MHz, DMSO-d\({}_{6}\)) \(\delta\) = 9.1 (s, 1H, NCHN), 7.76 (s,1H, NCH), 7.7 (s, 1H, NCH), 4.21 (t, \(J\) = 7.1 Hz, 2H, NCH\({}_{2}\)), 3.85 (s, 3H, NCH\({}_{3}\)), 1.77 (m, 2H, CH\({}_{2}\)), 1.27 (dq, \(J\) = 14.7, 7.3 Hz, 2H, CH\({}_{2}\)), 0.91 (t, \(J\) = 7.4 Hz, 3H, but-CH\({}_{3}\)). \({}^{13}\)C[\({}^{1}\)H] NMR (101 MHz, DMSO-d\({}_{6}\)) \(\delta\) = 136.94, 124.12, 122.75, 48.99, 36.19, 31.86, 19.25, 13.76. \({}^{31}\)P[\({}^{1}\)H] NMR (162 MHz, DMSO-d\({}_{6}\)) \(\delta\) = \(-\)1.35 (minor), \(-\)4.60 (major). **(BuPy)3 PMo\({}_{12}\)O\({}_{40}\)**: H\({}_{3}\)PMo\({}_{12}\)O\({}_{40}\).21H\({}_{2}\)O (1 g, 0.45 mmol) was mixed with 1-butyl pyridinium bromide (0.28 g, 1.3 mmol) in 10 mL water at room temperature for 4 h. The light green salt formed was filtered and dried under vacuum. Yield: 95%, (C\({}_{9}\)H\({}_{14}\)N)\({}_{3}\)PMo\({}_{12}\)O\({}_{40}\) Anal. Calc: C, 16.5; H, 1.8; N, 1.88. Found: C, 18.36; H, 1.85; N, 2.49. IR (ATR, v(cm\({}^{-1}\))): 3150-2850 (CH), 1632 (C=C), 1485 (C-N), 1061 (P-O), 951 (Mo=O), 740-880 (Mo-O-Mo). \({}^{1}\)H NMR (400 MHz, DMSO-d\({}_{6}\)) \(\delta\) = 9.10 (d, \(J\) = 5.4 Hz, 1H, 2H, Py-CHN), 8.6 (t, \(J\) = 7.9 Hz, 1H, Py-CHN), 8.18 (t, \(J\) = 7.1 Hz, 2H, Pyr-CH), 4.62 (t, \(J\) = 7.5 Hz, 2H, NCH\({}_{2}\)), 1.92 (m, 2H, CH\({}_{2}\)), 1.31 (m, 2H, CH\({}_{2}\)), 0.93 (t, \(J\) = 7.3 Hz, 3H but-CH\({}_{3}\)). \({}^{13}\)C[\({}^{1}\)H] NMR (101 MHz, DMSO-d\({}_{6}\)) \(\delta\) = 145.71, 144.94, 128.35, 60.89, 32.91, 19.02, 13.56. \({}^{31}\)P[\({}^{1}\)H] NMR (162 MHz, DMSO-d\({}_{6}\)) \(\delta\) = \(-\)1.33 (minor), \(-\)4.13 (major). **(BuPy)4 PMo\({}_{11}\)VO\({}_{40}\)**: H\({}_{4}\)PMo\({}_{11}\)VO\({}_{40}\).28H\({}_{2}\)O (1 g, 0.43 mmol) was mixed with 1-butyl pyridinium bromide (0.37 g, 1.7 mmol) in 10 mL water at room temperature for 4 h. The yellow salt formed was filtered and dried under vacuum. Yield: 90%, (C\({}_{9}\)H\({}_{14}\)N)\({}_{4}\)PMo\({}_{11}\)VO\({}_{40}\) Anal. Calc: C, 15; H, 1.9; N, 1.91. Found: C, 15.71; H, 1.93; N, 2.11.