Dokument

Zusammenfassung:
Mit der Verwendung von Tripod-Liganden, die das Cu(I)-Zentrum wie ein Skorpionat-Ligand dreizähnig koordinieren, ist in dieser Doktorarbeit ein neues Konzept verfolgt worden, um Cu(I)-Komplexe rigider zu machen. Da solche Cu(I)-Tripod-Komplexe erst unzureichend auf ihre photophysikalischen Eigenschaften untersucht worden sind, sind in dieser Doktorarbeit mit Hilfe von quantenchemischen Rechnungen sowie photophysikalischen Messungen die Grundlagen dieser neuen Emitter-Klasse erforscht worden.

Bibliographie / References

1. Hz, 3H, H5). 13 C{ 1 H} (75.5 MHz, DMSO-d6): (ppm) = 150.8 (d, 3 JCP = 12.1 Hz, C6), 149.2 (d, 1 JCP = 107.5 Hz, C2), 138.6 (d, 3 JCP = 11.0 Hz, C4), 129.3 (d, 2 JCP = 24.3 Hz, C3), 127.3 (d, 4 JCP = 2.8 Hz, C5). 31 P{ 1 H} (161.9 MHz, DMSO-d6): (ppm) = 12.36. IR (ATR) / cm -1 : 1574 (m), 1442 (m), 1425 (m), 1364 (w), 1277 (w), 1245 (w), 1150 (w), 1126 (w), 1080 (w), 1045 (w), 1004 (m), 906 (w), 786 (m), 771 (m), 740 (s), 725 (m), 664 (s), 635 (m), 518 (ss), 445 (w), 434 (w), 413 (m), 384 (m). HRMS (ESI+, MeCN): m/z (%) = 401.0048 (100, [tpypsCu+MeCN] + benötigt 401.0046), 359.9786 (2, [tpypsCu] + benötigt 359.9780). XRD-Analyse: vorhanden.
2. Hz, 3H, H5). 13 C{ 1 H} (75.5 MHz, CDCl3): (ppm) = 151.4 (d, 3 JCP = 11.3 Hz, C6), 148.9
3. Hz, 3 J56 = 4.9 Hz, 4 J5P = 2.6 Hz, 4 J53 = 1.2 Hz, 3H, H5). 13 C{ 1 H} (75.5 MHz, DMSO-d6): (ppm) = 150.4 (d, 3 JCP = 13.7 Hz, C6), 150.1 (d, 1 JCP = 108.0 Hz, C2), 138.3 (d, 3 JCP =
4. Hz, 3H, H4), 7.72-7.82 (m, 3H, H5). 13 C{ 1 H} (75.5 MHz, DMSO-d6): (ppm) = 151.0 (d, 3 JCP = 13.1 Hz, C6), 149.9 (d, 1 JCP = 127.9 Hz, C2), 138.4 (d, 3 JCP = 9.5 Hz, C4), 129.1 (d, 2 JCP = 18.2 Hz, C3), 127.5 (d, 4 JCP = 2.7 Hz, C5). 31 P{ 1 H} (161.9 MHz, DMSO-d6): (ppm) =
5. Hz, C6), 150.6 (d, 1 JCP = 108.3 Hz, C2), 137.1 (d, 3 JCP = 11.6 Hz, C4), 129.5 (d, 2 JCP =
6. C 45.46, H 3.05, N 10.60, S 8.09 %). 1 H-NMR (300.1 MHz, CDCl3): (ppm) = 9.00-9.06 (m, 3H, H6), 8.73 (ddd, 3 J3P = 8.8 Hz, 3 J34 = 7.9 Hz, 3H, H3), 7.95 (dddd, 3 J43 = 7.8 Hz, 3 J45 =
7. Hz, C3), 126.3 (d, 4 JCP = 3.0 Hz, C5). 31 P{ 1 H} (121.5 MHz, CDCl3): (ppm) = 9.10. 1 H- NMR (300.1 MHz, DMSO-d6): (ppm) = 8.79 (d, 3 J65 = 4.7 Hz, 3H, H6), 8.55 (dd, 3H, H3), 8.19 (dddd, 3 J43 = 7.8 Hz, 3 J45 = 7.8 Hz, 4 J4P = 4.4 Hz, 4 J46 = 1.7 Hz, 3H, H4), 7.75 (dddd, 3 J54
8. Hergestellt aus CuCl (33 mg, 0.34 mmol, 1.0 eq) und tpyps (100 mg, 0.34 mmol, 1.0 eq)
9. Hergestellt aus CuBr (49 mg, 0.34 mmol, 1.0 eq) und tpyps (100 mg, 0.34 mmol, 1.0 eq)
10. Hz, 3 J45 = 7.8 Hz, 4 J4P = 3.9 Hz, 4 J46 = 1.5 Hz 3H, H4), 7.46-7.57 (m, 3H, H5). 13 C{ 1 H} (75.5 MHz, CDCl3): (ppm) = 151.4 (d, 3 JCP = 13.7 Hz, C6), 150.8 (d, 1 JCP = 130.0 Hz, C2), 137.1 (d, 3 JCP = 9.9 Hz, C4), 129.1 (d, 2 JCP = 18.4 Hz, C3), 126.8 (d, 4 JCP = 2.9 Hz, C5).
11. Hz, C4), 129.1 (d, 2 JCP = 18.4 Hz, C3), 126.8 (d, 4 JCP = 3.0 Hz, C5). 31 P{ 1 H} (101.3 MHz, CDCl3): (ppm) = −8.08. 1 H-NMR (300.1 MHz, DMSO-d6): (ppm) = 8.81 (d, 3 J65 = 4.8 Hz, 3H, H6), 8.36 (dd, 3H, H3), 8.19 (dddd, 3 J43 = 7.7 Hz, 3 J45 = 7.7 Hz, 4 J4P = 3.8 Hz, 4 J46 =
12. MeCN (8 mL); orangefarbenes Pulver. Ausbeute: 84 mg (0.18 mmol, 47 %).
13. in MeCN (8 mL); orange-rotes Pulver. Ausbeute: 25 mg (0.05 mmol, 17 %).
14. in MeCN (8 mL); rotes Pulver. Ausbeute: 89 mg (0.22 mmol, 65 %). Elementaranalyse:
15. Analyse: vorhanden.
16. Darstellung von [CuBr(tpyps)] (neu/ veröffentl. in Refs. 344, 378)
17. Darstellung von [CuCl(tpyps)] (neu/ veröffentl. in Refs. 344, 378)
18. Darstellung von [CuI(tpypo)] (neu/ veröffentl. in Refs. 344, 378)
19. Darstellung von [CuI(tpypse)] (neu/ veröffentl. in Refs. 344, 378)
20. Darstellung von [CuI(tpyps)] (neu/ veröffentl. in Refs. 344, 378)
21. H} (100.6 MHz, DMSO-d6): (ppm) = 150.4 (d, 3 JCP = 12.4 Hz, C6), 149.6 (d, 1 JCP =
22. Hz, C4), 129.5 (d, 2 JCP = 24.6 Hz, C3), 126.4 (d, 4 JCP = 3.0 Hz, C5). 31 P{ 1 H} (121.5 MHz, CDCl3): (ppm) = 9.67. 1 H-NMR (300.1 MHz, DMSO-d6): (ppm) = 8.78-8.85 (m, 3H, H6), 8.65 (dd, 3H, H3), 8.21 (dddd, 3 J43 = 7.9 Hz, 3 J45 = 7.9 Hz, 4 J4P = 4.3 Hz, 4 J46 = 1.7 Hz, 3H, H4), 7.77 (dddd, 3 J54 = 7.6 Hz, 3 J56 = 4.9 Hz, 5 J5P = 2.5 Hz, 4 J53 = 1.3 Hz, 3H, H5).
23. in MeCN (8 mL); tiefrotes Pulver. Ausbeute: 99 mg (0.22 mmol, 65 %).
24. H} (101.3 MHz, CDCl3): (ppm) = −9.29. IR (ATR) / cm -1 : 1579 (w), 1435 (m), 1325 (w), 1275 (w), 1223 (m), 1144 (m), 1080 (w), 1049 (w), 1004 (w), 914 (w), 878 (w), 829 (w), 779 (m), 741 (s), 687 (w), 642 (w), 538 (ss), 454 (m), 411 (m), 304 (m), 278 (w), 254 (m), 207 (m), 191 (s), 150 (m), 124 (m), 106 (m), 59 (ss), 54 (ss), 40 (ss).
25. MeCN (8 mL); orange-rotes Pulver. Ausbeute: 97 mg (0.20 mmol, 57 %).
26. Hz, C5). 31 P{ 1 H} (161.9 MHz, DMSO-d6): (ppm) = 11.96. IR (ATR) / cm -1 : 1574 (m), 1440 (m), 1426 (m), 1279 (m), 1153 (w), 1126 (m), 1081 (m), 1044 (m), 1003 (m), 771 (m), 739 (s), 726 (m), 661 (s), 634 (m), 518 (ss), 436 (m), 408 (m), 382 (m). HRMS (ESI+, MeCN): m/z (%) = 401.0042 (100, [tpypsCu+MeCN] + benötigt 401.0046). XRD-
27. MHz, CDCl3): (ppm) = 151.5 (d, 3 JCP = 12.0 Hz, C6), 150.3 (d, 1 JCP = 107.9 Hz, C2), 137.4
28. XRD-Analyse: vorhanden.

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