Phosphoric acid Loaded Azo (-N=N-) based Covalent Organic

Framework for Proton Conduction

Suman Chandraa,† Tanay Kundua,† Sharath Kandambetha, Ravichandar BabaRaob, Yogesh Marathea,
Shrikant M. Kunjira and Rahul Banerjeea*
a
Physical/Materials Chemistry Division, CSIR- National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411008, India
b
Materials Science and Engineering Division, Commonwealth Scientific and Industrial Research Organization (CSIRO),
Clayton, Victoria 3168, Australia

Supporting Information
Section Page No
S-1 General Information S2
S-2 Synthetic Procedures S3
S-3 Structural Modeling and Powder X-Ray Diffraction Analysis S4
S-4 FT-IR Spectra S10
13
S-5 C CP/MAS NMR Spectra S11
S-6 Gas and Water Adsorption Studies of COFs S12
S-7 Pore size distribution of COFs S13
S-8 Thermo Gravimetric Analysis (TGA) S14
S-9 Scanning Electron Micrographs (SEM) S15
S-10 Transmission Electron Micrographs (TEM) S16
S-11 Stability studies of COFs S17
S-12 UV-Vis spectra S20
S-13 Proton Conductivity Studies of COFs S23
S-14 References S26

S1
 Section S-1: General Information

General Remarks: 1,3,5-triformylphloroglucinol was prepared from Phloroglucinol using

literature procedure1. All other reagents and solvents were commercially available and used as
received. Powder X-ray diffraction (PXRD) patterns were recorded on a Rigaku, MicroMax-
007HF with high intensity Microfocus rotating anode X-ray generator. All the samples were
recorded in the (2θ) range of 2–40 degrees and data was collected with the help of Control Win
software. A Rigaku, R-axis IV++ detector was employed in wide-angle experiments. The
radiation used was Cu Kα (1.54 Å) with a Ni filter, and the data collection was carried out using
an aluminium holder. Fourier transform infrared (FT-IR) spectra were taken on a Bruker Optics
ALPHA-E spectrometer with a universal Zn-Se ATR (attenuated total reflection) accessory in
the 600−4000 cm–1 region or using a Diamond ATR (Golden Gate). Thermo gravimetric
analyses (TGA) were carried out on a TG50 analyzer (Mettler-Toledo) or a SDT Q600 TG-DTA
analyzer under N2 atmosphere at a heating rate of 5 ºC min–1 within a temperature range of
25−900 °C. SEM images were obtained with a Zeiss DSM 950 scanning electron microscope and
FEI, QUANTA 200 3D Scanning Electron Microscope with tungsten filament as electron source
operated at 10 kV. The samples were sputtered with Au (nano-sized film) prior to imaging by a
SCD 040 Balzers Union. TEM images were recorded using FEI Tecnai G2 F20 X-TWIN TEM at
an accelerating voltage of 200 kV. The TEM Samples were prepared by dropcasting the sample
from isopropanol on copper grids TEM Window (TED PELLA, INC. 200 mesh). All gas
adsorption experiments (up to 1 bar) were performed on a Quantachrome Quadrasorb automatic
volumetric instrument. Solid state NMR (SSNMR) was taken in a Bruker 300 MHz NMR
spectrometer and Ligand NMR data were taken in Bruker 200 MHz NMR spectrometer. 31P CP-
MAS NMR spectra were recorded with Bruker AVENCE 300 MHz Spectrometer equipped with
31
4-mm double-resonance probe, operating at 300.00 MHz for 1H and 121.442 MHz for P.
Typical NMR experimental conditions were as follows π/2 duration, 2µs; recycle delay, 5s;
spinning speed, 10KHz. Chemical shift externally referenced to ortho-phosphoric acid at 0.0
ppm. UV-VIS spectra were recorded using Carry Win 50 (Agilent Tech.) after dissolving the
materials in chloroform or acetonitrile-water medium.

S2
 Section S-2: Synthetic procedures

Synthesis of Tp-Azo and Tp-Stb:

The detail synthetic procedures for Tp-Azo and Tp-Stb are given below:

In the typical synthesis, a pyrex tube (o.d. × i.d. = 10 × 8 mm2 and length 18 cm) is charged with
triformylphloroglucinol (Tp) (0.3 mmol), corresponding diamine {[ 4,4′-azodianiline [Azo] and
4,4′-diaminostilbene dihydrochloride [Stb] } (0.45 mmol), 3 mL of dimethylacetamide and 3mL
of o-dichlorobenzene. This mixture was sonicated for 10 minutes in order to get a homogeneous
dispersion. The tube was then flash frozen at 77 K (liquid N2 bath) and degassed by three freeze-
pump-thaw cycles. The tube was sealed off and then heated at 120 °C for 3 days. A dark red
coloured precipitate was collected by centrifugation or filtration and washed with
dimethylacetamide thrice. The powder collected was then solvent exchanged with acetone 5-6
times and dried at 180 °C under vacuum for 12 hours to get corresponding COFs in ~75 %
isolated yield.

FT-IR (Tp-Azo, powder, cm-1): 1619 (w), 1568 (s), 1450 (m),1284 (w), 1240 (s), 1147 (s), 987
(w), 839 (m). Elemental Analysis; Anal. Calcld. For C9ON2H6: C, 68.35; H, 3.79; N, 17.72;
found: C, 48.12; H, 5.27; N, 11.12.

FT-IR (Tp-Stb, powder, cm-1): 1574 (s), 1518 (w), 1450 (s), 1255 (m), 991 (w), 958 (w), 824
(m). Elemental Analysis; Anal. Calcld. For C10H6ON: C, 76.92; H, 3.84; N, 8.97; found: C, 69.84;
H, 4.50; N, 7.89.

S3
 Section S-3: Structure Modeling and Atomic Coordinates of COFs.

Atomic positions and cell sizes of modeled COF layers were optimized using Self-Consistent
Charge Density Functional Tight-Binding (SCC-DFTB) Method. Stacking of layers are affected
by the Coulomb repulsion between the partial atomic charges in adjacent layers.2 Hence, we
performed Mulliken population analysis for the charges. The adjacent layers were shifted with
respect to each other in different directions in order to avoid Coulomb repulsion from charges
alike. Several possibilities were considered, however, the best was taken from comparison of
simulated PXRD pattern with the experimental. Interlayer separation was also determined from
the comparison of PXRD patterns. The fractional coordinates of Tp-Azo and Tp-Stb are given
in Table S1 and S2 respectively.

In order to elucidate the structure of these COFs and to calculate the unit cell parameters,
possible 2-D models were optimized using Density Functional Tight-Binding method. Several
stacking possibilities were considered for reasons reported in the literature.2 The experimental
PXRD patterns are agreeable with the simulated patterns of eclipsed stacking models (Figure S1
to S3 in ESI). Hence we propose structures having hexagonal space group (P6/m) for Tp-
Azo and Tp-Stb by comparing the experimental and simulated PXRD patterns. Refinements of
PXRD pattern were done using Reflex module of Material studio.3

S4
Figure S1: PXRD pattern of as-synthesized Tp-Azo (Green) compared with the eclipsed (Red)
and staggered (Black) stacking models.

Figure S2: Experimental refined PXRD profiles of Tp-Azo (Red) compared with an eclipsed
arrangement (Black); difference plot is given in (Green).

S5
 Change in unit cell parameters of Tp-Azo
Before refinement After refinement
Space group : P6/m Space group : P6/m
a = b = 31.5 Å, c=3.4919 Å a = b = 32.41347 ± 2.67957 Å,
c= 3.37096 ± 0.26188Å
α = 90, β = 90, γ = 120 α = 90, β = 90, γ =120

Table S1. Fractional atomic coordinates for the unit cell of Tp-Azo.

Tp-Azo
Hexagonal; P6/m
a = b =31.5 Å, c=3.49 Å,
α = 90, β = 90, γ = 120.
O1 0.29695 0.57697 0
N2 0.38245 0.58505 0
C3 0.31382 0.61757 0
C4 0.39342 0.63145 0
C5 0.41468 0.5699 0
C6 0.46145 0.59947 0
C7 0.49111 0.58277 0
C8 0.47494 0.53664 0
C9 0.42853 0.50701 0
C10 0.39878 0.52354 0
C11 0.36359 0.64675 0
H12 0.42849 0.65656 0
H13 0.47589 0.63531 0
H14 0.34922 0.55946 0
H15 0.36308 0.50007 0
H16 0.52692 0.60571 0
H17 0.41558 0.4712 0
N1 0.50627 0.52081 1

S6
Figure S3: PXRD pattern of as-synthesized Tp-Stb (Green) compared with the eclipsed (Red)
and staggered (Black) stacking models.

Figure S4: Experimental refine (Red) compared with simulated eclipsed (Black) PXRD profiles
of Tp-Stb; difference plot is given in (Green).

S7
 Change in unit cell parameters of Tp-Stb
Before refinement After refinement
Space group : P6/m Space group : P6/m
a = b = 30.5 Å, c = 3.4919 Å a = b = 30.34945 ± 0.11016 ,
c = 3.47702 ± 0.01286 Å
α = 90, β = 90, γ = 120 α = 90, β = 90, γ = 120

Table S2. Fractional atomic coordinates for the unit cell of Tp-Stb.

Tp-Stb
Hexagonal; P6/m;
a = b= 30.5; c = 3.4919;
α = β =90.0000; γ =120.0000.
O1 0.29695 0.57697 0
N2 0.38245 0.58505 0
C3 0.31382 0.61757 0
C4 0.39342 0.63145 0
C5 0.41468 0.5699 0
C6 0.46145 0.59947 0
C7 0.49111 0.58277 0
C8 0.47494 0.53664 0
C9 0.42853 0.50701 0
C10 0.39878 0.52354 0
C11 0.36359 0.64675 0
H12 0.42849 0.65656 0
H13 0.47589 0.63531 0
H14 0.34922 0.55946 0
H15 0.36308 0.50007 0
H16 0.52692 0.60571 0
H17 0.41558 0.4712 0
C12 0.50627 0.52081 1

S8
Energy calculation of eclipsed (AA) and staggered (AB) stacking model of Tp-
Stb:-
The total energies of the eclipsed and staggered models for Tp-Stb COFs were calculated using
dispersion–corrected semi-empirical DFT-D2 method.4 All calculations were performed using
Vienna ab initio simulation package (VASP)5,6 with a plane-wave energy cut-off of 800 eV and
k-point sampling at the gamma-point. The interaction between core and valence electrons were
described by the projector-augmented-wave (PAW) method and the generalized gradient
approximation (GGA) of Perdew-Burke-Ernzerhof (PBE)7 was used to parameterize the
exchange-correlation functional. The total DFT energies based on eclipsed and staggered model
for Tp-Stb are -1581.6239 and -1580.6413 eV, respectably. Hence the eclipsed model of Tp-Stb
has minimum energy and higher stability than staggered model, a phenomenon commonly
occurred in 2D COF materials8,9.

S9
 Section S-4: FT-IR Spectra

Figure S5: FT-IR spectra of Tp-Azo (Green), 4,4′-azodianiline (Azo) (Blue) and 1,3,5-
triformylphloroglucinol (Tp) (Red).

Figure S6: FT-IR spectra of Tp-Stb (Green), 4,4′-diaminostilbene dihydrochloride (Stb) (Blue)
and 1,3,5-triformylphloroglucinol (Tp) (Red).

S10
 Section S-5: 13C CP/MAS NMR Spectra

Figure S7: 13C CP-MAS spectrum comparison of as synthesized Tp-Azo (Black) with PA@Tp-
Azo (Red).

Figure S8: 13C CP-MAS spectrum of the reference compound Tp-Azo monomer = 2,4,6-tris(((4-
((E)-phenyldiazenyl)phenyl)amino)methylene)cyclohexane-1,3,5-trione (Blue) (* assign for
spinning side band).

S11
 Section S-6: Gas and Water Adsorption Studies of COFs

Figure S9: N2 adsorption (filled symbols) and desorption (empty symbols) isotherms of
PA@Tp-Azo and PA@Tp-Stb.

Figure S10: Water adsorption (filled symbols) and desorption (empty symbols) isotherms
comparison of PA@Tp-Azo and PA@Tp-Stb, collected up to P/Po=0.9 (STP) at 293 K.

S12
 Section S-7: Pore size distribution of COFs

Figure S11: Pore size distribution of Tp-Azo calculated by using DFT method.

Figure S12: Pore size distribution of Tp-Stb calculated by using DFT method.

S13
 Section S-8: Thermogravimetric Analysis (TGA)

Figure S13: TGA data of Tp-Azo (Black) in comparison with PA@Tp-Azo (Red) under N2
atmosphere.

Figure S14: TGA data of Tp-Stb (Black) in comparison with PA@Tp-Stb (Red) under N2
atmosphere.

S14
 Section S-9: Scanning Electron Micrographs (SEM)

Figure S15: SEM images of (a) Tp-Azo and (b) PA@Tp-Azo.

Figure S16: SEM images of (a) Tp-Stb and (b) PA@Tp-Stb.

S15
 Section S-10: Transmission Electron Micrographs (TEM)

Figure S17: TEM images of Tp-Azo at different magnifications.

Figure S18: TEM images of Tp-Stb at different magnifications.

S16
 Section S-11: Stability studies of COFs

Figure S19: Stability of Tp-Azo in acid.

Figure S20: Stability of Tp-Azo in base.

S17
Figure S21: FT-IR spectra showing stability of Tp-Azo after treatment in boiling water (100
°C), acid (1.5M H3PO4) and base (3M NaOH).

Figure S22: Stability of Tp-Stb in acid.

S18
Figure S23: Stability of Tp-Stb in base.

S19
 Section S-12: UV-Vis Spectra

Figure S24: Changes in the absorption spectra of 4-Aminoazobenzene (ca. 2.5x10 -5 M of the
azobenzene unit in CH3CN-H2O) with increasing concentration of H3PO4.

Figure S25: Changes in the absorption spectra of Tp-Azo monomer (ca. 2.5x10 -5 M of the
azobenzene unit in CH3CN-H2O) with increasing concentration of H3PO4.

S20
Figure S26: Changes in the absorption spectra of Tp-Azo monomer (ca. 2.5x10 -5 M of the
azobenzene unit in CHCl3) with increasing concentration of CF3CO2H.

Figure S27: Changes in the absorption spectra of TpBD monomer (ca. 2.5x10 -5 M in CHCl3)
with increasing concentration of CF3CO2H.

S21
Figure S28: Changes in the absorption spectra of Stilbene (ca. 2.5x10 -5 M in CH3CN-H2O) with
increasing concentration of H3PO4.

S22
 Section S-13: Proton Conductivity Studies of COFs
Proton Conductivities of the COFs were measured using Solartron 1287 Electrochemical
Interface with 1255B frequency response analyzer via quasi-four-probe method. ca.180mg of as-
synthesized samples were pressed in a pellet maker to obtain uniform pellets of 0.135-0.36 cm
thickness, which was subject to a) anhydrous chamber or b) humidification for 24h and
subsequently measured the conductivities at different conditions. Proton conductivity was
measured by the following equation; σ = L/(R.A) where σ = proton conductivity, L = thickness
of the pellet, R = resistance of the pellet and A = area of the pellet.

For high-temperature proton conductivity measurements, the pellets were inserted within a
anhydrous or humidified chamber, which was encircled with a controlled heating coil attached
with an automated temperature controller. The heat flow within the chamber was controlled by a
dimerstat and measured by an infrared temperature sensor accordingly, having a sensing
accuracy of ±0.5 °C.

Figure S29: a) Digital image of the pallet of Tp-Azo used for proton conductivity measurements
with dimension. b) Equivalent circuit model representation for the proton conduction in COFs.

Figure S30: a) Nyquist plots for PA@Tp-Azo in anhydrous condition at different temperatures.
b) Variation of proton conductivity as a function of temperature.

S23
Figure S31: a) Nyquist plots for PA@Tp-Azo in hydrous condition at different temperatures. b)
Variation of proton conductivity as a function of temperature.

Figure S32: a) Selected Nyquist plots for PA@Tp-Stb in hydrous condition at different
temperatures. b) Activation energy fitting for PA@Tp-Stb.

S24
Table S3: Comparison of proton conductivity of Tp-Azo and Tp-Stb with
MOFs:

Compound Name Conducti Ea Conditions References

vity
1 Nafion ® ~1 × 10-1 0.22 80°C, 98% RH J. Polym. Sci., Part
(Ref. 10) B: Polym. Phys.
2011, 49, 1437
2 H3PO4@PBI 5 × 10-2 60°C, 0% RH Chem. Mater.,
(Ref. 11) 2005, 17, 21, 5329
3 SPEEK 2 × 10-2 80°C, 98% RH J. Polym. Sci., Part
(Ref. 10) B: Polym. Phys.
2011, 49, 1437
4 H2SO4@MIL-101 6.0 × 10-2 0.42 80°C, 20% RH J. Am. Chem. Soc.
(Ref. 12) 2012, 134, 15640
5 (NH4)2(adp)[Zn2(ox)3] · 8 × 10-3 0.63 25°C, 98% RH J. Am. Chem. Soc.,
3H2O (Ref. 13) 2009 , 131, 9906
6 Fe(ox).2H2O 1.3 × 10-3 0.37 25°C, 98% RH J. Am. Chem. Soc.,
(Ref. 14) 2009, 131, 3144.
7 (NH4)4[MnCr2(ox)6]3.4H2 1.1 × 10-3 0.23 25°C, 98% RH J. Am. Chem. Soc.,
O (Ref. 15) 2011, 133, 15328.
8 Cucurbit[6]uril (CB[6]) 1.1 × 10-3 0.39 25°C, 98% RH Angew. Chem. Int.
(Ref. 16) Ed. 2011, 50, 7870.
9 H3PO4@MIL-101 3 × 10-3 0.42 150°C,0.13%RH J. Am. Chem. Soc.
(Ref. 12) 2012, 134, 15640
10 PA@Tp-Azo 9.9 × 10-4 0.11 25°C, 98% RH This Work

11 (β-PCMOF2(Tz)0.45) 5 × 10-4 0.51 150°C,0% RH Nat. Chem. 2009, 1,

(Ref. 17) 705.
12 Mg2(dobdc)3.0.35LiOiPr3. 3.1 × 10-4 0.14 25°C, 0% RH J. Am. Chem. Soc.,
0.25LiBF4. EC3. DEC 2011, 133, 14522.
(Ref. 18)
13 (H5C2)2(dtoa) Cu 1 × 10-4 25°C, 80% RH Bull. Chem. Soc.
(Ref. 19) Jpn. 2010, 83, 42
14 PA@Tp-Azo 6.7 × 10-5 67°C, 0% RH This Work

15 [Zn(l-LCl)(Cl)](H2O)2 4.45 × 10-5 0.34 28°C, 98% RH J. Am. Chem. Soc.,

(Ref. 20) 2011, 133, 17950.
16 PCMOF-3 3.5 × 10-5 0.17 25°C, 98% RH J. Am. Chem. Soc.
(Ref. 21) 2010, 132, 14055.
S25
17 PA@Tp-Stb 2.3 × 10-5 0.14 60°C, 98% RH This Work

18 [MIL-53(Fe)-(COOH)2] 2.0 × 10-6 0.21 25°C, 98% RH J. Am. Chem. Soc

(Ref. 22) 2011, 133, 2034.

The aforementioned table shed light on the comparison between prototypical MOFs and the new
COFs as proton conducting materials. Clearly, the state of the art polymer membranes have two
order higher proton conductivity than these COFs, while MOFs have one order higher to
comparable conductivity. The conductivity values in MOFs are highly dependent on the amount
and nature of the dopants used for enhancing conductivities. We presume similar control over
conductivity along with the boon of polymeric materials in COFs with higher dimensionality,
porosity and stability to facilitate higher loading of guest conductors in future.

Figure S33: comparison of proton conductivity of Tp-Azo and Tp-Stb compared with standard
proton conducting materials.

Section S-14: References

1) Chong, J. H.; Sauer, M.; Patrick, B. O.; MacLachlan, M. J.Org. Lett. 2003, 5, 3823.
2) Lukose, B.; Kuc, A.; Heine, T. Chem. Eur. J., 2011, 17, 2388.
3) Accelrys, Material Studio Release Notes, Release 4.2, Accelrys Software, San Diego
2006.

S26
4) Grimme, S. J. Comput. Chem. 2006, 27, 1787.
5) Kresse, G.; Furthmuller, J. Comput. Mater. Sci. 1996, 6, 15.
6) Kresse, G.; Hafner, J. Phys. Rev. B 1993, 48, 13115.
7) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865.
8) Feng, X.; Chen, L.; Honsho, Y.; Saengsawang, O.; Liu, L.; Wang, L.; Saeki, A.; Irle, S.;
Seki, S.; Dong,Y.; Jiang, D. Adv. Mater. 2012, 24, 3026.
9) Spitler, E. L.; Koo, B. T.; Novotney, J. L.; Colson, J. W.; Uribe-Romo, F. J.;
Gutierrez, G. D.; Clancy, P.; Dichtel, W. R. J. Am. Chem. Soc. 2011, 133,19416.
10) Wu, X.; Wang, X.; He, G.; Benziger, J. J. Polym. Sci., Part B: Polym. Phys. 2011, 49,
1437.
11) Xiao, L.; Zhang, H.; Scanlon, E.; Ramanathan, L. S.; Choe, E.; Rogers, D.; Apple, T.;
Benicewicz, B. C. Chem. Mater., 2005, 17, 5329.
12) Ponomareva, V. G.; Kovalenko,K. A.; Chupakhin, A. P.; Dybtsev, D. N.; Shutova, E. S.;
Fedin, V. P. J. Am. Chem. Soc.2012, 134, 15640.
13) Sadakiyo, M.; Yamada, T.; Kitagawa, H. J. Am. Chem. Soc., 2009, 131, 9906.
14) Yamada, T.; Sadakiyo, M.; Kitagawa, H. J. Am. Chem. Soc. 2009, 131, 3144.
15) Pardo, E.; Train, C.; Gontard. G.; Boubekeur, K.; Fabelo, O.; Liu, H.; Dkhil, B.; Lloret,
F.; Nakagawa, K.; Tokoro, H.; Ohkoshi, S.; Verdaguer, M. J. Am. Chem. Soc., 2011, 133,
15328.
16) Yoon, M.; Suh, K.; Kim, H.; Kim, Y.; Selvapalam, N.; Kim, K.; Angew. Chem., Int. Ed.
2011, 50, 7870.
17) Hurd, J. A.; Vaidhyanathan, R.; Thangadurai, V.; Ratcliffe, C. I.; Moudra-kovski, I. M.
and Shimizu, G. K. H.; Nat. Chem. 2009, 1, 705.
18) Wiers, B. M.; Foo, M.-L.; Balsara, N. P.; Long, J. R. J. Am. Chem. Soc. 2011, 133,
14522.
19) Yamada, T.; Morikawa, S.; Kitagawa, H. Bull. Chem. Soc. Jpn. 2010, 83, 42.
20) Sahoo, S. C.; Kundu, T.; Banerjee, R. J. Am. Chem. Soc., 2011, 133, 17950.
21) Taylor, J. M.; Mah, R. K.; Moudrakovski, I. L.; Ratcliffe, C. I.; Vaidhyanathan, R.;
Shimizu, G. K. H. J. Am. Chem. Soc. 2010, 132, 14055.
22) Shigematsu, A.; Yamada, T.; Kitagawa, H. J. Am. Chem. Soc. 2011, 133, 2034.

S27