of 32
S1
Ultrafast Wiggling and Jiggling: Ir
2
(1,8-diisocyanomenthane)
4
2+
Martin Pižl,
a,b
Bryan M. Hunter,
c
Gregory M. Greetham,
d
Michael Towrie,
d
Stanislav Záliš,
a,
*
Harry B. Gray,
c,
* Antonín Vlček
a,e,
*
a
J. Heyrovský Institute of Physical Chemistry, Acad
emy of Sciences of the Czech Republic,
Dolejškova 3, CZ-182 23 Prague, Czech Republic
b
Department of Inorganic Chemistry, University of C
hemistry and Technology, Prague,
Technická 5, CZ-166 28 Prague, Czech Republic
c
Beckman Institute, California Institute of Technol
ogy, Pasadena, CA 91125, USA
d
Central Laser Facility, Research Complex at Harwel
l, STFC, Rutherford Appleton Laboratory,
Harwell Oxford, Didcot, Oxfordshire OX11 0QX, Unite
d Kingdom,
e
Queen Mary University of London, School of Biologi
cal and Chemical Sciences, Mile End Road,
London E1 4NS, United Kingdom
e-mail: zalis@jh-inst.cas.cz, hbgray@caltech.edu,
a.vlcek@qmul.ac.uk
SUPPLEMENTARY INFORMATION
Contents
Figures
p. S2
Tables
p. S25
Quantum chemical calculations
p. S30
DFT-calculated low-frequency vibrations p. S30
Orientational isomerism
p. S31
References
p. S31
S2
FIGURES
Figure S1.
Representative Lorentzian fits of Ir(dimen) TRIR s
pectra in DCM (top) and MeCN
(bottom). 470 nm – excited spectra (left) fitted wi
th two Lorentzians, 585 nm – excited spectra
(right) fitted with three Lorentzians to include th
e 2202 cm
–1
bleach. Attempts to fit the spectra
with Voigt functions resulted in a Lorentzian shape
s with the Gaussian width vanishing.
-0.004
-0.002
0.000
0.002
0.004

Absorbance
470 nm
585 nm
50 fs
2 ps
250 ps
250 ps
2 ps
50 fs
-0.010
-0.005
0.000
0.005
0.010
-0.004
-0.002
0.000
0.002
0.004

Absorbance
-0.010
-0.005
0.000
0.005
0.010
2050
2100
2150
2200
-0.004
-0.002
0.000
0.002
0.004

Absorbance
Wavenumber / cm
-1
2050
2100
2150
2200
-0.010
-0.005
0.000
0.005
0.010
Wavenumber / cm
-1
-0.004
-0.002
0.000
0.002
0.004
470 nm

Absorbance
2 ps
250 ps
50 fs
585 nm
50 fs
2 ps
250 ps
50 fs
2 ps
250 ps
-0.0050
-0.0025
0.0000
0.0025
0.0050
-0.004
-0.002
0.000
0.002
0.004

Absorbance
-0.0050
-0.0025
0.0000
0.0025
0.0050
2050
2100
2150
2200
-0.004
-0.002
0.000
0.002
0.004

Absorbance
Wavenumber / cm
-1
2050
2100
2150
2200
-0.0050
-0.0025
0.0000
0.0025
0.0050
Wavenumber / cm
-1
S3
Figure S2.
Time-evolution of IR spectra of Ir(dimen) in MeCN
after 470 nm (left) and 585 nm
(right) excitation measured with a magic angle betw
een Vis pump and IR probe polarizations.
Detail of the 2130-2160 cm
–1
region. Top: Difference TRIR spectra measured at s
elected time
delays. Bottom: decay associated spectra obtained b
y multiexponential global fitting.
-0.003
-0.002
-0.001
0.000
0.001
0.002
0.003

Absorbance
0.2
3
15
400
Exp
Exp
DAS
-0.004
-0.002
0.000
0.002
0.004
0.2
3
15
400
2130
2140
2150
2160
-0.003
-0.002
-0.001
0.000
0.001
0.002
0.003
585 nm

Absorbance
Wavenumber / cm
-1
0.5
5
73
long
470 nm
DAS
2130
2140
2150
2160
-0.004
-0.002
0.000
0.002
0.004
Wavenumber / cm
-1
5
71
long
S4
Figure S3.
Time-evolution of IR spectra of Ir(dimen) in DCM a
fter 470 nm (left) and 585 nm
(right) excitation measured with a magic angle betw
een Vis pump and IR probe polarizations.
Top: Difference TRIR spectra measured at selected t
ime delays. Bottom: decay associated
spectra obtained by multiexponential global fitting
. The lower panel shows the detail of the
2130-2160 cm
–1
region.
-0.004
-0.002
0.000
0.002
0.004
DAS
DAS
Exp

Absorbance
0.2
3
15
400
Exp
-0.009
-0.006
-0.003
0.000
0.003
0.006
0.009
0.2
3
15
400
2080
2120
2160
2200
-0.004
-0.002
0.000
0.002
0.004

Absorbance
Wavenumber / cm
-1
0.6
6.6
108
long
2080
2120
2160
2200
-0.009
-0.006
-0.003
0.000
0.003
0.006
0.009
580 nm
Wavenumber / cm
-1
6.4
110
long
470 nm
-0.004
-0.002
0.000
0.002
0.004
DAS
DAS
Exp

Absorbance
0.2
3
15
400
Exp
-0.009
-0.006
-0.003
0.000
0.003
0.006
0.009
0.2
3
15
400
2130
2140
2150
2160
-0.004
-0.002
0.000
0.002
0.004

Absorbance
Wavenumber / cm
-1
0.6
6.6
108
long
2130
2140
2150
2160
-0.009
-0.006
-0.003
0.000
0.003
0.006
0.009
580 nm
Wavenumber / cm
-1
6.4
110
long
470 nm
S5
Figure S4.
Time-evolution of IR spectra of Ir(dimen) in THF a
fter 470 nm (left) and 585 nm
(right) excitation measured with a magic angle betw
een Vis pump and IR probe polarizations.
Top: Difference TRIR spectra measured at selected t
ime delays. Bottom: decay associated
spectra obtained by multiexponential global fitting
. The lower panel shows the detail of the
2130-2160 cm
–1
region.
-0.0010
-0.0005
0.0000
0.0005
0.0010

Absorbance
0.2
3
20
400
Exp
DAS
DAS
Exp
-0.002
-0.001
0.000
0.001
0.002
0.2
3
20
400
2080
2120
2160
2200
-0.0010
-0.0005
0.0000
0.0005
0.0010

Absorbance
Wavenumber / cm
-1
0.6
7.6
102
long
470 nm
585 nm
2080
2120
2160
2200
-0.002
-0.001
0.000
0.001
0.002
Wavenumber / cm
-1
8.2
105
long
-0.0010
-0.0005
0.0000
0.0005
0.0010

Absorbance
0.2
3
20
400
Exp
DAS
DAS
Exp
-0.002
-0.001
0.000
0.001
0.002
0.2
3
20
400
2130
2140
2150
2160
-0.0010
-0.0005
0.0000
0.0005
0.0010

Absorbance
Wavenumber / cm
-1
0.6
7.6
102
long
470 nm
585 nm
2130
2140
2150
2160
-0.002
-0.001
0.000
0.001
0.002
Wavenumber / cm
-1
8.2
105
long
S6
Figure S5.
Time dependences of the maximum wavenumber of the
transient IR band of
Ir(dimen) in MeCN after 470 and 585 nm excitation a
t a magic angle polarization.
0.0 0.4 0.8 1.2 1.6 2.0
2135
2136
2137
2138
2139
Peak wavenumber / cm
-1
Time / ps
470 nm, magic
585 nm, magic
S7
Figure S6.
Difference evolution associated (EA) spectra obtai
ned by multiexponential global
fitting of Ir(dimen) TRIR spectra in MeCN, DCM, and
THF measured upon 470 nm (left) and 585
nm (right) excitation with a magic angle between Vi
s pump and IR probe polarizations. EA
spectra can be approximately regarded as difference
IR spectra at the beginning of the
associated kinetics step.
-0.0030
-0.0015
0.0000
0.0015
0.0030
585 nm
0.5
5
73
long
470 nm
MeCN
-0.004
-0.002
0.000
0.002
0.004
5
71
long
-0.004
-0.002
0.000
0.002
0.004
THF
DCM

Absorbance
0.6
6.6
108
long
THF
DCM
MeCN
-0.009
-0.006
-0.003
0.000
0.003
0.006
0.009
6.4
110
long
2080
2120
2160
2200
-0.0008
-0.0004
0.0000
0.0004
0.0008

Absorbance

Absorbance
Wavenumber / cm
-1
0.6
7.6
102
long
2080
2120
2160
2200
-0.002
-0.001
0.000
0.001
0.002
Wavenumber / cm
-1
8.2
105
long
S8
Figure S7.
Representative Lorentzian fits of ISC and "long" E
A spectra to determine positions
and widths of
ν
(C
N) IR bands of Ir(dimen)
1
d
σ
*p
σ
and
3
d
σ
*p
σ
excited states, respectively.
Top: in DCM. Bottom: in MeCN. 470 nm – excited spec
tra (left) fitted with two Lorentzians, 585
nm – excited spectra (right) fitted with three Lore
ntzians to include the 2202 cm
–1
bleach.
-0.004
-0.002
0.000
0.002
0.004
585 nm

Absorbance
108 ps
long
long
109 ps
470 nm
-0.010
-0.005
0.000
0.005
0.010
2050
2100
2150
2200
-0.004
-0.002
0.000
0.002
0.004

Absorbance
Wavenumber / cm
-1
2050
2100
2150
2200
-0.010
-0.005
0.000
0.005
0.010
Wavenumber / cm
-1
-0.004
-0.002
0.000
0.002
0.004

Absorbance
-0.006
-0.004
-0.002
0.000
0.002
0.004
0.006
2050
2100
2150
2200
-0.004
-0.002
0.000
0.002
0.004

Absorbance
Wavenumber / cm
-1
73 ps
long
long
72 ps
585 nm
470 nm
2050
2100
2150
2200
-0.006
-0.004
-0.002
0.000
0.002
0.004
0.006
Wavenumber / cm
-1
S9
Figure S8.
Time-evolution of IR spectra of Ir(dimen) in MeCN a
fter 470 nm (left) and 585 nm
excitation (right) obtained with parallel (top) and
perpendicular (bottom) orientations of pump
and probe polarization directions.
-0.002
0.000
0.002

Absorbance
0.2
3.5
15
400
-0.004
-0.002
0.000
0.002
0.004
0.2
3.5
15
400
2080
2120
2160
2200
-0.002
0.000
0.002

Absorbance
Wavenumber / cm
-1
1
7
68
long
470 nm, parallel
585 nm, parallel
2080
2120
2160
2200
-0.004
-0.002
0.000
0.002
0.004
Wavenumber / cm
-1
7.9
79
long
Exp
Exp
DAS
DAS
-0.003
-0.002
-0.001
0.000
0.001
0.002

Absorbance
0.1
2.5
15
400
470 nm, perpendicular
585 nm, perpendicular
-0.006
-0.003
0.000
0.003
0.1
2.5
15
400
2080
2120
2160
2200
-0.002
-0.001
0.000
0.001
0.002

Absorbance
Wavenumber / cm
-1
0.3
4.7
70
long
2080
2120
2160
2200
-0.003
0.000
0.003
Wavenumber / cm
-1
4.5
68
long
Exp
DAS
DAS
Exp
S10
Figure S9.
Time-evolution of IR spectra of Ir(dimen) in DCM af
ter 470 nm (left) and 585 nm
excitation (right) obtained with parallel (top) and
perpendicular (bottom) orientations of pump
and probe polarization directions.
-0.0030
-0.0015
0.0000
0.0015
0.0030

Absorbance
0.2
3.5
25
500
470 nm, parallel
585 nm, parallel
Exp
DAS
DAS
Exp
-0.004
-0.002
0.000
0.002
0.004
0.2
3.5
25
500
2080
2120
2160
2200
-0.0030
-0.0015
0.0000
0.0015
0.0030

Absorbance
Wavenumber / cm
-1
1
8.2
111
long
2080
2120
2160
2200
-0.004
-0.002
0.000
0.002
0.004
Wavenumber / cm
-1
11.2
122
long
-0.004
-0.002
0.000
0.002

Absorbance
0.2
3
25
500
-0.006
-0.003
0.000
0.003
0.006
0.2
3
25
500
2080
2120
2160
2200
-0.002
0.000
0.002

Absorbance
Wavenumber / cm
-1
0.5
7.2
100
long
470 nm, perpendicular
585 nm, perpendicular
Exp
DAS
DAS
Exp
2080
2120
2160
2200
-0.006
-0.003
0.000
0.003
0.006
Wavenumber / cm
-1
6.2
107
long
S11
Figure S10a.
Selected kinetics traces of Ir(dimen) in DCM measur
ed after 470 nm and 585 nm
excitation with magic angle between pump and probe
beam polarizations. Top: 3-point
averaging applied. Bottom: raw data. Traces in the
left panel were measured at (from top
down): 2109, 2106, 2103, 2101, 2098, 2095, 2093, 20
90, 2087, 2085, 2082 cm
–1
, break line,
2221, 2215, 2206 cm
–1
. Right panel: 2103, 2101, 2098, 2095, 2093, 2090,
2087, 2085, 2082,
2079, 2077, 2074, 2071 cm
–1
, break line, 2215, 2209, 2188, 2185, 2182, 2180 cm
–1
.
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0000
0.0002
0.0004
0.0006

Absorbance
Time / ps
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0006
-0.0004
-0.0002
0.0000
0.0002
0.0004
0.0006
0.0008
Time / ps
470 nm
585 nm
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0002
0.0000
0.0002
0.0004
0.0006

Absorbance
Time / ps
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0006
-0.0004
-0.0002
0.0000
0.0002
0.0004
0.0006
0.0008
Time / ps
S12
Figure S10b.
Selected kinetics traces of Ir(dimen) in DCM measur
ed after 470 nm and 585 nm
excitation with parallel pump and probe beam polari
zations. Top: 3-point averaging applied.
Bottom: raw data. Traces in the left panel were mea
sured at (from top down): 2112, 2109,
2104, 2098, 2093, 2082, 2071 cm
–1
, break line, 2209, 2182 cm
–1
. Right panel: 2109, 2106, 2104,
2101, 2098, 2095, 2093, 2090, 2087, 2085, 2082, 207
9, 2069 cm
–1
, break line, 2221, 2215, 2212,
2209, 2206, 2197 cm
–1
.
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0002
0.0000
0.0002
0.0004
0.0006

Absorbance
Time / ps
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0006
-0.0004
-0.0002
0.0000
0.0002
0.0004
0.0006
0.0008
Time / ps
470 nm
585 nm
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0002
0.0000
0.0002
0.0004
0.0006

Absorbance
Time / ps
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0006
-0.0004
-0.0002
0.0000
0.0002
0.0004
0.0006
0.0008
Time / ps
S13
Figure S10c.
Selected kinetics traces of Ir(dimen) in DCM measur
ed after 470 nm and 585 nm
excitation with perpendicular pump and probe beam p
olarizations. Top: 3-point averaging
applied. Bottom: raw data. Traces in the left panel
were measured at (from top down): 2098,
2095, 2093, 2090, 2087, 2085, 2082, 2079, 2074, 206
3 cm
–1
, break line, 2215, 2203, 2197, 2191
cm
–1
. Right panel: 2104, 2101, 2098, 2095, 2093, 2090,
2087, 2085, 2082, 2079, 2077 cm
–1
,
break line, 2212, 2209, 2206, 2200, 2194 cm
–1
.
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0004
-0.0002
0.0000
0.0002
0.0004
0.0006
0.0008
Time / ps
470 nm
585 nm
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0002
0.0000
0.0002
0.0004

Absorbance
Time / ps
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0002
0.0000
0.0002
0.0004

Absorbance
Time / ps
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-0.0004
-0.0002
0.0000
0.0002
0.0004
0.0006
0.0008
Time / ps