of 6
S1
Supporting Information
For
Charge Photoinjection in Intercalated and Covalentl
y Bound
[Re(CO)
3
(dppz)(py)]
+
-DNA Constructs Monitored by Time Resolved Visible
and Infrared Spectroscopy
Eric D. Olmon,
Pamela A. Sontz,
Ana María Blanco-Rodríguez,
Michael Towrie,
§
Ian P. Clark,
§
Antonín Vl
č
ek, Jr.,*
,‡
and Jacqueline K. Barton*
,†
Division of Chemistry and Chemical Engineering, California Institute of
Technology, Pasadena,
California 91125, USA;
Queen Mary University of London, School of Biological and Chemical Sciences,
Mile End Road, London E1 4NS, United Kingdom;
§
Central Laser Facility, STFC Rutherford Appleton
Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX, United Kingdom
CONTENTS
:
Pg. S2
Strand sequences and MALDI data.
Pg. S3
Steady-state emission spectra of Re
-OEt with DNA.
Pg. S4
Lifetime distributions from maximum entropy analysis of emission R
e
-OH with DNA.
Pg. S5
Picosecond-timescale TRIR difference spectra of Re-25(I) and Re-
25(G).
Pg. S6
Nanosecond-timescale TRIR difference spectra of Re
-OH with GC-30 from 1550 cm
-1
to
1750 cm
-1
.
S2
Strand sequences and MALDI data.
Strand
Sequence
Mass (calc.)
Mass (MALDI)
ATa
5
-TTT ATA TTA TTA AAT AAA TTT TAT ATA TTT-3
9172
9165
ATb
3
-AAA TAT AAT AAT TTA TTT AAA ATA TAT AAA-5
9226
9222
GCa
5
-CCC GCG CCG CCG GGC GGG CCC CGC GCG CCC-3
9094
9094
GCb
3
-GGG CGC GGC GGC CCG CCC GGG GCG CGC GGG-5
9334
9333
Re-25(G)a
5
-Re
-AGC GTT GGT GAC TGA CTG ACT GAC T-3
8583
8582
Re-25(G)b
3
-TCG CAA CCA CTG ACT GAC TGA CTG A-5
7611
7614
Re-25(I)a
5
-Re
-AIC ITT GGT GAC TGA CTG ACT GAC T-3
8553
8550
Re-25(I)b
3
-TCI CAA CCA CTG ACT GAC TGA CTG A-5
7596
7597
S3
FIGURE S1
Figure S1
. Steady-state emission spectra of 20

M Re
-OEt in the presence of 0.5 mM (base pairs) AT-30
(red), and of 0.5 mM (base pairs) AT-30 (black) alone following excitation at 355
nm. Samples were
prepared in D
2
O buffer (10 mM NaP
i
, 50 mM NaCl; pD 7.0).
S4
FIGURE S2
Figure S2
. Lifetime distributions from maximum entropy analysis of emission from (
64

M) Re
-OH in
the presence of 1.6 mM (base pairs) DNA and of 64

M Re-25(I) or Re-25(G) measured on the
picosecond timescale (
λ
ex
= 355 nm, 1 ps pulse width). Samples were prepared in D
2
O buffer (10 mM
NaP
i
, 50 mM NaCl; pD 7.0) and were irradiated at 355 nm. Probability P is plotted as a f
unction of rate k.
Large distributions at k = 10
11
-10
12
s
-1
are caused by convolution of the measurement signal with
instrumental noise. The emission decay from Re
-OH in buffer is expected to be monoexponential; the
complex distribution of rates observed here may be due to the formation of aggregat
es (solubility is quite
low) or it may simply be an effect of the low emission intensity observed for
this sample.
S5
FIGURE S3
Figure S3
. Picosecond-timescale TRIR difference spectra of 100

M Re-25(I) (top) and Re-25(G)
(bottom) measured at the indicated delay times after 355 nm, 50 fs excitation. E
ach probe data point is
separated by ca. 2.1 cm
-1
. Arrows indicate changes in the spectra with time. Delay times displa
yed are a
subset of the data collected.
S6
FIGURE S4
Figure S4
. Nanosecond-timescale TRIR difference spectra showing changes in the I
R absorbance of 4.8
mM (base pairs) GC-30 in the presence of 0.5 mM Re
-OH following excitation at 355 nm. Arrows
indicate changes in the spectra with time. The increase in absorbance
at ~1700 cm
-1
is clearly displayed.