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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).


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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-


{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-


{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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