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Supplementary Information
Multi-emitting Properties of Hybrid Langmuir-Blodgett Films of
Amphiphilic Iridium Complexes and the Exfoliated Nanosheets of
Saponite Clay
Hisako Sato,a Kenji Tamura,b Keishi Oharaa and Shin-ichi Nagaokaa
aDepartment of Chemistry, Graduate School of Science and Engineering, Ehime University, Matsuyama
790-8577, Japan,
bNational Institute of Materials Science, Tsukuba 305-0044, Japan
Electronic Supplementary Material (ESI) for New Journal of ChemistryThis journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2013
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1. 1H NMR and mass spectroscopy data of iridium(III) complexes
[Ir(dfppy)2(dc9bpy)]ClO4
1H NMR (chloroform-d, 400MHz, 25 °C): 9.43 (s, 2H), 8.30 (d, J = 8.8 Hz, 2H), 7.81 (dd, J = 6.0, 6.0
Hz, 2H), 7.71 (d, J = 6.0 Hz, 2H), 7.50 (d, J = 5.7 Hz, 2H), 7.23 (d, J = 5.7 Hz, 2H), 7.09 (dd, J = 6.0,
6.0 Hz, 2H), 6.55 (ddd, J = 9.3, 9.3, 2.5 Hz, 2H), 5.68 (dd, J = 6.0, 2.0 Hz, 2H), 2.99 (t, J = 7.7 Hz, 4H),
1,71 (tt, J = 7.7, 7.7 Hz, 4H), 1.42-1.20 (overlapped, 24H), 0.86 (t, J = 6.8 Hz, 6H)
MS (m/z; FAB): 981.41 (calculated for [Ir(dfppy)2(dc9bpy)]+; C50H56F4IrN4), 980 (experimentally
obtained).
[Ir(ppy)2(dc9bpy)]ClO4
1H NMR (chloroform-d, 400 MHz, 25 °C): 8.76 (s, 2H), 7.89 (d, J = 7.9 Hz, 2H), 7.78-7.72
(overlapped, 4H), 7.66 (d, J = 7.9, 0.9 Hz, 2H), 7.54 (d, J = 5.8 Hz, 2H), 7.17 (dd, J = 5.8, 1.5 Hz, 2H),
7.06-6.98 (overlapped, 4H), 6.90 (dd, J = 7.5, 7.5 Hz, 2H), 6.29 (d, J = 7.9, 0.9 Hz, 2H), 2.90 (t, J = 7.7
Hz, 4H), 1.70 (tt, J = 7.7, 7.7, 4H), 1.42-1.20 (overlapped, 24H), 0.87 (t, J = 6.7 Hz, 6H)
MS (m/z; FAB): 909.44 (calculated for [Ir(ppy)2(dc9bpy)]+; C50H60IrN4), 910 (experimentally obtained).
[Ir(piq)2(dc9bpy)]ClO4
1H NMR (chloroform-d, 400 MHz, 25 °C): δ 8.93 (t, J = 5.43Hz, 2H), 8.70 (s, 2H), 8.25 (d, J = 7.99 Hz,
2H), 7.92 (t, J = 4.33 Hz, 2H), 7.77 (t, J = 4.39 Hz, 4H), 7.54 (t, J = 5.61 Hz, 2H), 7.43 (dd, J = 6.47 Hz,
4H), 7.13 (m, J = 5.92 Hz, 4H), 6.89 (t, J = 7.44Hz, 2H), 6.28 (d, J = 6.71 Hz, 2H), 2.91 (t, J = 7.99 Hz,
4H), 1.25 (s, 28H), 0.87 (t, J = 6.89 Hz, 6H)
MS (m/z; FAB): 1009.4 (calculated for [Ir(piq)2(dc9bpy)]+; C58H64IrN4) 1007 (experimentally obtained).
Electronic Supplementary Material (ESI) for New Journal of ChemistryThis journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2013
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2. The electronic absorption spectra of iridium(III) complexes in methanol
Figure S1. The UV-visible spectra of [Ir(dfppy)2(dc9bpy)]ClO4 (blue), [Ir(ppy)2(dc9bpy)]ClO4 (black)
and [Ir(piq)2(dc9bpy)] ClO4 (red) in methanol.
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3. The AFM images of the hybrid films deposited onto glass substrates
Figure S2. The AFM images of the hybrid single-layered films deposited onto glass substrates at 10
mNm-1: (a) {DFPPY/SAP} , (b) {PPY/SAP} and (c) {PIQ/SAP}.
Figure S3. The AFM images of the hybrid triple-layered films deposited onto glass substrates at 10
mNm-1: (a) {PIQ/SAP/DFPPY/SAP/PPY/SAP}, (b) {DFPPY/SAP/PPY/SAP/PIQ/SAP} and (c)
{PIQ/SAP/PPY/SAP/DFPPY/SAP}.
(a) {DFPPY/SAP} (b) {PPY/SAP} (c) {PIQ/SAP}
(a) (b) (c)
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4. The UV-visible spectra of single-, double- and triple-layered hybrid films
Figure S4. The UV-visible spectra of the hybrid LB films deposited onto quartz substrates: (a) the
single-layer films: {DFPPY/SAP} (blue), {PPY/SAP} (green) and {PIQ/SAP} (red); (b) the double-
layered films: {DFPPY/SAP/PPY/SAP} (sky blue), {PPY/SAP/DFPPY/SAP} (orange),
{PPY/SAP/PIQ/SAP} (gray), {PIQ/SAP/PPY/SAP} (yellow), {DFPPY/SAP/PIQ/SAP} (blue), and
{PIQ/SAP/DFPPY/SAP} (green); (c) the triple-layered films: {PPY/SAP/DFPPY/PIQ/SAP} (sky blue),
{PIQ/SAP/DFPPY/SAP/PPY/SAP} (orange), {DFPPY/SAP/PPY/SAP/PIQ/SAP} (gray),
{PIQ/SAP/PPY/SAP/DFPPY} (yellow), {DFPPY/SAP/PIQ/SAP/PPY/SAP} (blue), and
{PPY/SAP/PIQ/SAP/DFPPY/SAP} (green).
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5. The emission spectra of the single-layered hybrid film containing a 1:1:1 mixture of DFPPY,
PPY and PIQ (denoted by {DFPPY, PPY, PIQ/SAP})
Figure S5. The emission spectra of {DFPPY, PPY, PIQ/SAP} in vacuum and under the oxygen
atmosphere. The excitation wavelength was 430 nm. The vertical axis denotes the intensity of emission
at an arbitrary unit: a (in vacuum), b (at 1 kPa of oxygen pressure), c (at 4 kPa), d (at 11 kPa), e (at 27
kPa), f (at 53 kPa) and g (at 101.3 kPa), respectively.
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6. Emission spectra of the heterogeneous double-layered films
Figure S6. The emission spectra of the hybrid double-layered films of (a){PPY/SAP/DFPPY/SAP},
(b){PIQ/SAP/DFPPY/SAP}, (c){PPY/SAP/PIQ/SAP} and (d){PIQ/SAP/PPY/SAP}. An oxygen gas
was introduced at various pressures. The excitation wavelength was 430 nm. The vertical axis denotes
the intensity of luminescence at an arbitrary unit: a (in vacuum), b (at 1 kPa of oxygen pressure), c (at 4
kPa), d (at 11 kPa), e (at 27 kPa), f (at 53 kPa) and g (at 101.3 kPa), respectively.
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7. The quantitative analyses of the emission spectra of the double-layered hybrid films with
various deposition orders:
(a) The analyses of energy transfer processes in the heterogeneous double-layered hybrid films in
vacuum: The following equation was applied to analyze the energy transfer processes in the double-
layered hybrid films:
)()101
1011()()1()( 00 aETA
A
dETET FFFa
d
(S1),
in which FET() is the profile of the emission spectrum of a double-layered film, Fd0
() the profile of
the emission spectrum of a single-layered film of a donor, Fa0() the profile of the emission spectrum of
a single-layered film of an acceptor, ET the energy transfer efficiency from a donor to an acceptor, (or
) the contribution of the quenching efficiency due to the presence of a clay layer and Ad (or Aa) the
absorbance of an acceptor film (or an donor film) at 430 nm, respectively. The parameters of ET, and
were chosen to attain the best fit of the calculated emission spectrum, FET(), with the experimental
one.
Table S1 Summary of the parameters for energy transfer and quenching processes in the double-
layered hybrid films.
Parameters {DFPPY/SAP/
PPY/SAP}
{PPY/SAP/
DFPPY/SAP}
{DFPPY/SAP/
PIQ/SAP}
{PIQ/SAP/
DFPPY/SAP}
{PPY/SAP/
PIQ/SAP}
{PIQ/SAP/
PPY/SAP}
ET 1.0 1.0 0.99 0.99 0.90 0.90
0.0 0.0 0.0 0.0 0.0 0.0
-0.12 -0.12 -1.5 -1.5 -1.5 -1.5
Ad 0.00017 0.00017 0.00017 0.00017 0.00096 0.00096
Aa 0.00096 0.00096 0.00165 0.00165 0.00165 0.00165
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(b) The reconstruction of the emission spectra of the double-layered heterogeneous hybrid films
according to equation (S1) in the supporting information.
Figure S7. The emission spectra of the hybrid double-layered films reconstructed in terms of the sum of
the emission spectra of two components in vacuum. The films are double-layered hybrid of
(a){DFPPY/SAP/PPY/SAP}, (b) {PPY/SAP/DFPPY/SAP},(c){DFPPY/SAP/PIQ/SAP},
(d){PIQ/SAP/DFPPY/SAP}, (e){PPY/SAP/PIQ/SAP} and (f){PIQ/SAP/PPY/SAP}. The blue solid and
orange curves are for the observed and calculated spectra, respectively
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8. The reconstruction of the observed emission spectra of the triple-layered heterogeneous hybrid
films according to equation (1) in the text
Figure S8. The emission spectra of the triple-layered hybrid films reconstructed in terms of the sum of
the emission spectra of three components in vacuum. The films are the triple-layered hybrid films: (a)
{PPY/SAP/DFPPY/SAP/PIQ/SAP}, (b) {PIQ/SAP/DFPPY/SAP/PPY/SAP}, (c)
{DFPPY/SAP/PPY/SAP/PIQ/SAP}, (d) {PIQ/SAP/PPY/SAP/DFPPY/SAP}, (e)
{DFPPY/SAP/PIQ/SAP/PPY/SAP}, and (f) {PPY/SAP/PIQ/SAP/DFPPY/SAP}. Blue solid and orange
curves are the observed and calculated spectra, respectively.
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8. The Stern-Volmer plots for quenching by oxygen molecules in case of the single- and double-
layered hybrid films
Figure S9. The Stern-Volmer plots for quenching by oxygen molecules in case of the single- (left) and
double-layered (right) hybrid films: (left) (a) {DFPPY/SAP}, (b) {PPY/SAP} and (c) {PIQ/SAP};
(right) (a) {DFPPY/SAP/PPY/SAP}, (b) {PPY/SAP/DFPPY/SAP}, (c) {DFPPY/SAP/PIQ/SAP}, (d)
{PIQ/SAP/DFPPY/SAP}, (e) {PPY/SAP/PIQ/SAP}, and (f) {PIQ/SAP/PPY/SAP}. The curves are
fitted by equation (2) in the text.
Table S2. The Stern-Volmer parameters for quenching by oxygen molecules in case of the single-
layered hybrid films
{DFPPY/SAP} {PPY/SAP} {PIQ/SAP}
Ksv1 0.002 0.002 0.0006
Ksv2 0.24 0.27 0.065
f1 0.18 0.17 0.61
f2 0.82 0.83 0.39
Ksvav 0.2 0.23 0.026
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Table S3. The Stern-Volmer parameters for quenching by oxygen molecules in case of the double-
layered hybrid films
{DFPPY/SAP
PPY/SAP}
{PPY/SAP
DFPPY/SAP}
{DFPPY/SAP
PIQ/SAP}
{PIQ/SAP
DFPPY/SAP}
{PPY/SAP
PIQ/SAP}
{PIQ/SAP
PPY/SAP}
Ksv1 0.0017 0.0019 0.0020 0.002 0.0019 0.0010
Ksv2 0.15 0.2 0.075 0.072 0.082 0.093
f1 0.56 0.35 0.59 0.54 0.52 0.76
f2 0.44 0.65 0.41 0.46 0.48 0.24
Ksvav 0.06 0.13 0.03 0.03 0.04 0.02
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