Table 1. Experimental Vibrational Frequencies (in cm–1) of the [Ru(bpy)3]+ and [Ru(bpy)3]2+ Systems Compared with Scaled Harmonic Values Computed at the M06 Levela.
| theory |
|||
|---|---|---|---|
| experiment (IRMPD) | M06/6-311+G(d,p) | M06/TZ2P | assignmentsb |
| [Ru(bpy)3]2+ | |||
| 1583 | 1602 | CC str (s), CN str (w) | |
| 1436 (25) | 1424 | 1451 | CC str (s), CN str (w), CHip bend (s) |
| 1389 | 1437 | CHip bend (s), CC str (s), CN str (w) | |
| 757 (9) | 750 | 763 | CHoop bend (s), bpy ring breath (w) |
| [Ru(bpy)3]+ | |||
| 1549 (∼50) | 1550 | 1538 | CC str (s), CN str (w), CHip bend (s) |
| 1427 (33) | 1422 | 1425 | CC str (w), CN str (w), CHip bend (s) |
| 1360 (47) | 1343 | 1342 | |
| 1264c (∼50) | 1278 | 1240 | NRuN bend (s), CC str (s), CN str (s) |
| 1213 (∼42) | 1226 | 1219 | CHip bend (s), CC str (w) |
| 1215 | 1213 | CHip bend (s), CC str (w) | |
| 1073 (60) | 1093 | 1093 | bpy ring breath (w), CHip bend (w) |
| 870 (100) | 917 | 899 | Ru–N sym str (s), bpy ring breath (s), CHip bend (w) |
| 846 | 855 | bpy-oop (m), CHoop bend (w) | |
| 746 (11) | 743 | 758 | NRuN bend (s), bpy ring breath (s), CHoop (s) |
| 627 (41) | 615 | 635 | Ru–N asym str (s), bpy ring deformation (s) |
a
Values in parentheses are observed IR bandwidths (FWHM in cm–1). Mode descriptions for the IR bands indicate the dominant contributions.
b
str, stretch; ip, in-plane bending mode; oop, out-of-plane bending; bpy ring breath, bipyridine ring breathing; sym, symmetric; asym, asymmetric; s, strong band; m, medium; w, weak.
c
Shoulder.