Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.
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Supplementary Information for Photoinduced Structural Distortions and Singlet-­‐Triplet Intersystem Crossing in Cu(I) MLCT Excited States Monitored by Optically Gated Fluorescence Spectroscopy Sofia Garakyaraghi,1 Petr Koutnik1 and Felix N. Castellano1* Department of Chemistry, North Carolina State University, Raleigh, NC 27695-­‐8204, United States Contents (1) Representative sub-­‐picosecond time-­‐resolved photoluminescence decay kinetics of [Cu(dsbp)2]+ in CH2Cl2 at room temperature. (2) Representative sub-­‐picosecond of time-­‐resolved photoluminescence decay kinetics of [Cu(dsbtmp)2]+ in CH2Cl2 at room temperature. (3) Representative sub-­‐picosecond of time-­‐resolved photoluminescence decay kinetics of [Cu(diptmp)2]+ in CH2Cl2 at room temperature. S1 (1) Representative sub-­‐picosecond time-­‐resolved photoluminescence decay kinetics of [Cu(dsbp)2]+ in CH2Cl2 at room temperature. [Cu(dsbp)2]+ in dichloromethane (λex = 440 nm) -T1
τ1 = 0.26 (1.0)
525 nm
τ1 = 0.30 (1.0)
550 nm
τ1 = 0.38 (0.87)
575 nm
Intensity (Counts)
τ2 = 3.7 (0.13)
τ1 = 0.89 (0.64)
600 nm
τ2 = 6.2 (0.36)
τ1 = 0.73 (0.44)
625 nm
τ2 = 6.8 (0.56)
650 nm
τ1 = 6.3 (1.0)
τ1 = 6.2 (1.0)
0
5
10
15
Time (ps)
675 nm
20
25
]+ in dichloromethane measured by fluorescence-­‐
Figure S1. Time-­‐resolved PL decay kinetics of [Cu(dsbp)2
upconversion method at room temperature. The black line represents the most adequate fit to a (sum of) exponential function(s), with the time constants (amplitudes) provided in the legend. S2 (2) Representative sub-­‐picosecond time-­‐resolved photoluminescence decay kinetics of [Cu(dsbtmp)2]+ in CH2Cl2 at room temperature. [Cu(dsbtmp)2]+ in dichloromethane (λex = 440 nm) -T3
τ1 = 0.26 (1.0)
525 nm
τ1 = 0.26 (1.0)
550 nm
τ1 = 0.33 (0.92)
575 nm
Intensity (Counts)
τ2 = 2.7 (0.07)
τ1 = 0.99 (0.34)
600 nm
τ2 = 3.4 (0.66)
τ1 = 4.2 (1.0)
625 nm
τ1 = 3.5 (1.0)
650 nm
675 nm
τ1 = 4.3 (1.0)
0
2
4
6
8
10
Time (ps)
12
14
16
]+ in dichloromethane measured by fluorescence-­‐
Figure S2. Time-­‐resolved PL decay kinetics of [Cu(dsbtmp)2
upconversion method at room temperature. The black line represents the most adequate fit to a (sum of) exponential function(s), with the time constants (amplitudes) provided in the legend. S3 (3) Representative sub-­‐picosecond time-­‐resolved photoluminescence decay kinetics of [Cu(diptmp)2]+ in CH2Cl2 at room temperature. [Cu(diptmp)2]+ in dichloromethane (λex = 440 nm) -T2
τ1 = 0.37 (1.0)
525 nm
τ1 = 0.32 (0.99)
550 nm
τ2 = 3.2 (0.01)
575 nm
τ1 = 0.4 (0.84)
Intensity (Counts)
τ2 = 3.1 (0.16)
0
2
4
6
τ1 = 2.7 (1.0)
600 nm
τ1 = 3.8 (1.0)
625 nm
τ1 = 3.5 (1.0)
650 nm
τ1 = 3.4 (1.0)
675 nm
8
Time (ps)
10
12
14
Figure S3. Time-­‐resolved PL decay kinetics of [Cu(diptmp)2]+ in dichloromethane measured by fluorescence-­‐
upconversion method at room temperature. The black line represents the most adequate fit to a (sum of) exponential function(s), with the time constants (amplitudes) provided in the legend. S4