Supporting Information

Highly conductive nanostructured PEDOT polymer confined

into the mesoporous MIL-100(Fe)

Pablo Salcedo-Abraira,a† Andrea Santiago-Portillo,b† Pedro Atienzar,b Pierre Bordet,c

Fabrice Salles,d Nathalie Guillou,e Erik Elkaim,f Hermenegildo García,b Sergio

Navalon,b,* Patricia Horcajadaa,*

aAdvanced Porous Materials Unit, IMDEA Energy, Avda. Ramón y Cajal 3, 28935

Móstoles-Madrid, Spain

bDepartment of Chemistry and Instituto de Tecnología Química, Consejo Superior de

Investigaciones Científicas-Universitat Politècnica de València, Universitat Politècnica

de València, C/Camino de Vera, s/n, 46022, Valencia, Spain

cInstitute NEEL CNRS/UGA, 25 rue des Martyrs, Grenoble cedex 9, France.

dInstitut Charles Gerhardt Montpellier, UMR 5253 CNRS UM ENSCM, Université

Montpellier, Place E. Bataillon, 34095 Montpellier Cedex 05, France

eInstitut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles St-Quentin

en Yvelines, Université Paris Saclav, 45 Av. des Etats-Unis, 78035 Versailles, France

fCRISTAL Beamline, Synchrotron Soleil, L'orme des Merisiers, Saint-Aubin, BP 48,

91192 Gif-sur-Yvette Cedex, France

† These authors contributed to this manuscript equally

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2019

100 200 300 400 500 6000

20

40

60

80

100

MIL-100 (Fe)

Acetonitrile

58.0

18.43

Weig

ht

loss (

%)

T (ºC)

27.81

74.94

82.5

45.2

68.3

22.6

Hexane

Figure S1.TGA curves of PEDOT@MIL-100(Fe) encapsulated in acetonitrile (blue) or hexane

(red), together with the empty MIL-100(Fe) solid (black)

100 200 300 400 500 6000

20

40

60

80

100

90% (w/w) EDOT

180% (w/w) EDOT

18.4322.65

Weig

ht

loss (

%)

T (ºC)

81.6980.00

45.2

56.76

12.87

91.5

31.58

45% (w/w) EDOT

Figure S2. TGA curves of PEDOT@MIL-100 (Fe)-1 (blue), 2 (red) and 3 (orange) composites

4000 3000 2000 1000

PEDOT

PEDOT (180 wt%)/MIL100Fe-hex

PEDOT (45 wt%)/MIL100Fe-hex

PEDOT (90 wt%)/MIL100Fe-hex

PEDOT (90 wt%)/MIL100Fe-acet

Tra

nsm

itta

nce (

%)

Wavenumber (cm-1)

MIL100Fe

Figure S3. FTIR spectra of MIL-100(Fe) (a), PEDOT-MIL100(Fe)-1 (b), PEDOT-MIL100(Fe)-

2 (c), PEDOT-MIL100(Fe)-3 (d) and as-prepared PEDOT (c).

Figure S4. PXRD patterns of MIL-100(Fe) (Black) and PEDOT@MIL-100(Fe)-1 (pink), 2

(red) and-3 (green) composites.

Table S1. Elemental composition of free PEDOT and amount of PEDOT inside the MIL-

100(Fe)-2

Theo. vs exp.

Free PEDOT Fe/S at. ratio 0 vs 0,08 ± 0,05

Free PEDOT Cl/S at. ratio 0,3 vs 0,33 ± 0,12

PEDOT@MIL-

100(Fe)-2.

PEDOT (%wt; dry empty solid) 60 ± 9

Number of EDOT monomer/u.c. 1062 ± 174

Number EDOT monomer/large cage 58 ± 9

Number EDOT monomer/small cage 37 ± 6

Number total Cl/u.c. 1365 ± 363

Cl/S at. Ratio 1.28 ± 0.33

Considering 1 Cl- / 3 EDOT 354 ± 58

Number excess Cl/u.c. 1011 ± 319

Number Fe total/u.c. 2003 ± 581

Number Fe MIL100/u.c. 1152

Number Fe excess/u.c. 851 ± 581

Excess Fe/Fe MIL100 (u.c.) 0,74 ± 0,50

Figure S5. XPS of MIL-100(Fe). Legend: (a) C 1s; (b) O 1s; (c) Fe 2p; (d) Cl 2p; (e) F 1s.

282 284 286 288 290 292 2940

20000

40000

60000

80000

100000C

PS

Binding energy (eV)

Csp2

O=C-O

525 530 535 540

20000

40000

60000

80000

100000

120000

140000

CP

S

Binding energy (eV)

185 190 195 200 205 210 215 220

4800

5200

5600

6000

6400

CP

S

Binding energy (eV)

680 685 690 695 70067500

70000

72500

75000

77500

CP

S

Binding energy (eV)

a) b)

c) d)

e)

710 720 730

70000

80000

90000

100000

110000

120000

130000

CP

S

Binding energy (eV)

Fe(III)

Fe(III) satellites

Figure S6. XPS of PEDOT@MIL-100(Fe)-2. Legend: (a) C 1s; (b) O 1s; (c) Fe 2p; (d) Cl 2p;

(e) F 1s; (f) S 2p

Figure S7. PXRD patterns collected by using synchrotron radiation

Figure S8. Left: Simulated and experimental PDF analysis of EDOT molecule. Right: DFT

Simulated chemical structure of isolated EDOT together with the main atomic distances.

Figure S9. Top: experimental PDFs of EDOT and PEDOT up to 10 (left) and 25 Å (right).

Bottom: DFT simulated chemical structure of free PEDOT together with the main atomic

distances. Sulphur, carbon, oxygen, hydrogen and chlorine are in yellow, grey, red, white and

blue respectively.

Figure S10. Comparison of the PDFs of MIL-100(Fe) and PEDOT@MIL-100(Fe).

Figure S11. Top: Subtracted PDF contribution of the EDOT in the EDOT@MIL-100(Fe)

compared with the free EDOT. Bottom: Subtracted PDF contribution of the PEDOT in the

PEDOT@MIL-100(Fe)-2 compared with the free PEDOT. Sulphur, carbon, oxygen, hydrogen

and iron are in yellow, grey, red, white and purple respectively

Figure S12. a) FTIR spectra of MIL-100(Fe) (red), PEDOT@MIL-100(Fe)-2 (black) and

isolated PEDOT (blue) (Asterisk indicate the presence of PEDOT bands in PEDOT@MIL-

100(Fe)) and b) zoom of the selected areas.

Figure S13. XRD patterns of: a) PEDOT@MIL-100(Fe)-2 thin film on FTO before (bottom)

and after (up) of 50 cycles of cyclic voltammetry and b) PEDOT@MIL-100(Fe)-2 thin film on

FTO before (bottom) and after (up) of 20 cycles of electrochromic switching. Asterisk indicate

diffraction peaks corresponding to the MIL-100(Fe) material.

Figure S14 SEM-EDX analysis of the PEDOT-MIL-100(Fe)-2 flat surface supported on FTO

employed for cyclic voltammetry measurements (left) and for electrochromism measurements

(right).

Figure S15. SEM-EDX analysis of the PEDOT-MIL-100(Fe)-2 film thickness supported on

FTO employed for cyclic voltammetry measurements (left) and for electrochromism

measurements (right)

Figure S16. FIB-SEM images of: (a) the fresh PEDOT@MIL-100(Fe)-2 film; (b) the used

PEDOT@MIL-101(Fe)-2 sample after 50 cycles of voltammetry; PEDOT@MIL-100(Fe)-2

before (c) and after (d) used in the 50 cycles of the cyclic voltammetry. Note: fast SEM images

were recorded (c,d) with low quality on purpose to properly measure the thickness minimizing

possible error due to the movement of the sample.

Figure S17. AFM images of PEDOT@MIL-100(Fe)-2 film before (a) and after (b) 50 cyclic

voltammetry cycles and roughness estimation.

Roughness (Ra) 301 nm

Roughness (Ra) 356 nm

a)

b)

Figure S18: Result of the fit of the PDF from the Ni standard sample.

Figure S19: Conformations of the PEDOT investigated by DFT calculations

Figure S20: Model of MIL-100 from literature (Horcajada et al., Chem. Commun., 2007, 2820-

2822)