Whereas spin-orbit effects modify the spectrum of the tri-substituted
phenylpyridine reference complex 1 (Fig. 1), they do not change significantly the
absorption properties of the carbonyl/halide substituted complex 2 which is not
discussed in this contribution.
Scheme 1 Optimized structures of fac-[Ir (ppy) 3 ] 1 and cis-[Ir (ppy) 2 (CO)(Cl)] 2 (data from [80])
E25 A22
A23 A24
E12 E13
Wavelength [nm]
Intensity
250
45000
50
45
40
35
30
25
20
15
10
5
0
40000 35000 30000
Wavenumber [cm -1 ]
25000 20000 15000
lr(ppy) 3
[10 3
I - moI -1
cm -1
]
300
350 400
500 600 700
A11 A12
E3 E5 E6 E7
A2
A5 A6
A28 A29
E30
40000
Intensity in arbitrary unit
35000
30000
Energy in cm -1
25000
20000
15000
ε
Fig. 1 TD-DFT/PW91 “spin-orbit” absorption spectrum of fac-[Ir (ppy) 3 ] 1 compared to the
experimental one (in inset). The “spin-free” spectrum is represented by dotted line and the main
bands are assigned according to the A n and E n “spin-orbit” states generated by the splitting of the
lowest triplet states T n and their mixing with the singlet S n states (Table 2) (reprinted with
permission from Brahim and Daniel [80] Copyright 2014 Elsevier)
386
C. Daniel