Molecules 2013, 18
8971
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(DBU) (234 mg, 1.54 mmol) yielded complex 5 as a dark red solid (184 mg, 96%). H-NMR (300
MHz, CD3CN): δ 9.08 (s, 2H, H3′ of terpy-N3), 8.86 (d, 2H, J = 8.0 Hz, H3′ of 1), 8.80–8.69 (m, 3H, H3
of terpy-N3, H4′ of 1), 8.59 (d, 4H, J = 8.0 Hz, H3 of 1), 8.25–8.18 (m, 6H, H4 and Hb of terpy-N3, H4
of 1), 7.78 (d, 2H, J = 8.1 Hz, Ha of terpy-N3), 7.68 (d, 2H, J = 5.3 Hz, H6 of terpy-N3), 7.59 (d, 2H,
J = 5.2 Hz, H6 of 1), 7.51–7.49 (m, 4H, H5 of 1 and H5 of terpy-N3), 4.65 (s, 2H, -CH2-). 13C (75 MHz,
CD3CN): δ 158.9, 155.7, 155.6, 154.5, 154.3, 144.7, 143.8, 134.8, 130.8, 130.6, 129.9, 128.4, 127.6,
+
125.3, 54.6. HRMS (ESI): m/z 1080.1305 ([M−PF6]+, C37H27F12IrN9P2 requires 1080.1302). FT-IR
(ATR): υ/cm−1 3647w, 3092w, 2102m (N3), 1609m, 1480m, 1456m, 1405w, 1250m, 1034m, 825s (PF6).
Synthesis of bis(4′-(4-azidomethylphenyl)-2,2′:6′,2′′-terpyridine)iridium(III)tris(hexafluorophosphate)
(6). Using general method C, bis(4′-(4-hydroxymethylphenyl)-2,2′:6′:2′′-terpyridine)iridium(III)tris
(hexafluorophosphate) 4 (75 mg, 0.055 mmol), diphenylphosphorylazide (DPPA) (125 µL, 0.580 mmol),
and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (100 µL, 0.670 mmol) yielded complex 6 as red
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crystals (55 mg, 70%). H-NMR (300 MHz, acetone-d6): δ 9.10 (s, 4H, H3′), 8.72 (d, 4H, J = 7.8 Hz,
H3), 8.26–8.21 (m, 8H, H4 and Hb), 7.80 (d, 4H, J = 8.4 Hz, Ha), 7.70 (d, 4H, J = 5.2 Hz, H6), 7.61 (dd,
4H, H5, coupling constants too close to allow determination of their exact values), 4.65 (s, 4H,
-CH2N3). 13C-NMR (75 MHz, CD3CN): δ 159.0, 156.5, 155.6, 154.4, 143.8, 141.1, 136.3, 130.6,
+
129.9, 128.4, 125.3, 54.6. HRMS (ESI): m/z 1211.1806 ([M−PF6]+, C44H32F12IrN12P2 requires
+
1211.1786). MS (ESI): m/z 1211.28 ([M−PF6]+, C44H32F12IrN12P2 requires 1211.18). IR (KBr) υ/cm−1:
3629w, 3110w, 2361w, 2336w, 2097m (s, N3), 1684m, 1653m, 1558m, 1506m, 1479m, 1437m, 1254m,
1033m, 1016m, 838s (PF6).
Synthesis of (1-((1-(4-(2,2':6',2"-terpyridine)benzyl)-1H-1,2,3-triazol-4-yl)methyl)-1H-pyrrole-2,5-
dione)(2,2':6',2''-terpyridine)iridium(III)tris(hexafluorophosphate) (7). Using general method D,
(2,2':6',2''-terpyridine)(4'-(4-azidomethylphenyl)-2,2':6',2''-terpyridine)iridium(III)tris(hexafluorophosphate)
5 (30 mg, 0.0245 mmol), 1-(2-propynyl)-1H-pyrrole-2,5-dione 9 (3.5 mg, 0.026 mmol), copper
sulphate (30 mg, 0.044 mmol) and ascorbic acid (22 mg, 0.057 mmol) gave complex 7 as a yellow
powder (28 mg, 84%): mp > 300 °C; 1H-NMR (300 MHz, CD3CN): δ 9.05 (s, 2H, H3′ of terpy-triazole),
8.86 (dd, 2H, J = 8.2, 1.9 Hz, H3′ of terpy), 8.77 (dd, 1H, J = 8.1, 2.6 Hz, H4′ of terpy), 8.68 (dd, 2H,
J = 7.8, 0.6 Hz, H6 of terpy-triazole), 8.58 (dd, 4H, J = 8.1, 0.7 Hz, H6 of terpy), 8.25–8.17 (m, 6H, H5,
Ha of 3-Az, H4 of terpy), 7.69–7.66 (m, 4H, Hb, H3 of terpy-triazole), 7.58 (dd, 2H, J = 5.7, 1.0 Hz, H3
of terpy), 7.50–7.45 (m, 4H, H5 of terpy and H4 of terpy-triazole), 6.82 (s, 2H, 2CH pyrrole), 5.73 (s,
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2H, -CH2-), 4.75 (s, 2H, -CH2-). C (75 MHz, CD3CN): δ 158.90, 155.70, 155.56, 154.46, 154.28,
144.69, 143.84, 134.79, 130.78, 130.59, 129.88, 128.38, 127.59, 125.32, 54.58, 33.65. HRMS (ESI):
+
m/z 1215.1636 ([M−PF6]+, C44H32F12IrN10O2P2 requires 1215.1623). FT-IR (ATR): υ/cm−1 3542br,
3091w, 2262s, 1715w, 1632w, 1483w, 1437w, 1193w, 1036m, 846s (PF6).
Synthesis of bis(1-((1-(4-(2,2':6',2"-terpyridine)benzyl)-1H-1,2,3-triazol-4-yl)methyl)-1H-pyrrole-2,5-
dione)iridium(III)tris(hexafluorophosphate) (8). Using general method D, bis(4′-(4-azidomethylphenyl)-
2,2':6',2''-terpyridine)iridium(III)tris(hexafluorophosphate) 6 (20 mg, 0.015 mmol), 1-(2-propynyl)-
1H-pyrrole-2,5-dione 9 (10 mg, 0.074 mmol), copper sulphate (4.3 mg, 0.17 mmol) and ascorbic acid
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(2.5 mg, 0.142 mmol) gave complex 8 as a yellow solid (6 mg, 24%). m.p. >300 °C. H-NMR