Lattice expansion of highly oriented 2D phthalocyanine covalent organic framework films

Article abstract of DOI:10.1002/anie.201107070

Expanding into application: Covalent organic framework (COF) films are ideally suited for vertical charge transport and serve as precursors of ordered heterojunctions. Their pores, however, were previously too small to accommodate continuous networks of c

Full text of DOI:10.1002/anie.201107070

Supporting Information
ꢀ Wiley-VCH 2012
69451 Weinheim, Germany
Lattice Expansion of Highly Oriented 2D Phthalocyanine Covalent
Organic Framework Films**
Eric L. Spitler, John W. Colson, Fernando J. Uribe-Romo, Arthur R. Woll, Marissa R. Giovino,
Abraham Saldivar, and William R. Dichtel*
anie_201107070_sm_miscellaneous_information.pdf

Supporting Information
Table of Contents
A. Materials and Instrumentation
S-2
S-5
B. Synthetic Procedures
C. NMR Spectra
S-11
S-15
S-20
S-21
S-30
S-31
S-37
S-39
S-40
D. FTIR Spectra
E. UV-Vis-NIR Characterization
F. Simulation & Refinement of the COF Structures
G. Thermogravimetric Analysis
H. Surface Area Measurements
I. Scanning Electron Microscopy
J. Higher Resolution X-ray Reflectivity of ZnPc-DPB COF Film
K. References
S-1

A. Materials. All reagents were purchased from commercial sources and used without
further purification. Zn octahydroxyphthalocyanine 5,1 pyrene diboronic acid 1,2 and
diphenylbutadiyne diboronic acid 23 were prepared via literature procedures. 1,4-Dioxane
and propionic acid were purchased from commercial sources and used without further
purification. Other solvents were purchased from commercial sources and purified using
a custom-built alumina-column based solvent purification system.
Instrumentation.
Infrared spectra were recorded on a Thermo Nicolet iS10 with a diamond ATR
attachment and are uncorrected.
UV/Vis absorbance spectra were recorded on a Cary 5000 UV-Vis-NIR
spectrophotometer with a mercury lamp in either dichloromethane solution or as solids
using a praying mantis diffuse reflectance accessory. Emission and excitation spectra
were recorded on a Horiba Jobin Yvon Fluorolog-3 fluorescence spectrophotometer
equipped with a 450 W Xe lamp, double excitation and double emission
monochromators, a digital photon-counting photomultiplier and a secondary InGaAs
detector for the NIR range. Correction for variations in lamp intensity over time and
wavelength was achieved with a solid-state silicon photodiode as the reference. The
spectra were further corrected for variations in photomultiplier response over wavelength
and for the path difference between the sample and the reference by multiplication with
emission correction curves generated on the instrument. Solid samples were mounted
between quartz slides and mounted on a solid sample holder, and emission was observed
using a front face detection accessory.
X-ray diffraction patterns were recorded on a Rigaku Smartlab Powder X-Ray
Diffractometer in 2θ medium resolution parallel beam/PSA mode employing CuKαꢀlines
focused radiation at 40 kV, 44 mA power and equipped with a Ge crystal detector fitted
with a 0.5 mm radiation entrance slit. Samples were mounted on zero background sample
holders by dropping powders from a wide-blade spatula and then leveling the sample
surface with a glass microscope slide. No sample grinding or sieving was used prior to
analysis. Samples were observed using a 0.045º 2θꢀstep scan from 1.0 – 34º (Omega =
1.0º) with an exposure time of 0.4 s per step. No peaks could be resolved from the
baseline for 2θꢀ> 34º data, which was therefore not considered for further analysis.
S-2

Thermogravimetric analysis from 20-600 °C was carried out on a TA Instruments
Q500 Thermogravimetric Analyzer in an N2 atmosphere using a 10 °C/min ramp without
equilibration delay.
Scanning electron microscopy (SEM) was performed on a FEI Strata 400 FE-SEM.
Materials were deposited onto a sticky carbon surface on a flat aluminum platform
sample holder. No metal sputtering of the sample was necessary. Focused ion beam (FIB)
patterning and milling was performed using a FEI Strata 400 FIB Ga+ LIM system. A
1x10 µm Pt strip (~1 µm thickness) was deposited using the electron gun onto COF films
grown on SLG/SiO2 substrates prior to exposing the sample to the FIB. The sample was
then milled with the FIB using a cleaning cross-section. After milling, the samples were
imaged at 2 keV using the electron gun. Cross-sectional images were obtained using a
stage tilt angle of 52°. Thickness measurements made at this angle were corrected by
multiplying by 1.26. SLG/SiO2 substrates were grounded to the sample holder using
sticky carbon prior to imaging to minimize charging.
Mass spectra were obtained on a Waters MALDI micro MX MALDI-TOF mass
spectrometer using positive ionization and a reflectron detector. MALDI samples were
prepared by wet deposition of a saturated analyte/dithranol matrix solution onto a
metallic sample plate and air dried before loading into the instrument.
Surface area measurements were conducted on a Micromeritics ASAP 2020
Accelerated Surface Area and Porosimetry Analyzer using ca. 20 mg samples degassed at
180 °C for 12 hours. Nitrogen isotherms were generated by incremental exposure to ultra
high purity nitrogen up to ca. 1 atm over 28-hour periods in a liquid nitrogen (77 K) bath,
and surface parameters were determined using BET adsorption models included in the
instrument software (Micromeritics ASAP 2020 V1.05) using the P/P0 ranges according
to consistency criteria for the BET model in frameworks.4 Non-local density functional
theory (NLDFT) model for N2 at 77 K and oxide surface with cylindrical pore shape
integrated in the Micromeritics data reduction software was used to calculate pore size
distribution curves from the adsorption branch of the measures isotherms.
NMR spectra were recorded on a Bruker ARX 300 MHz spectrometer using a
standard 1H/X Z-PFG probe at ambient temperature with a 20 Hz sample spin rate.
S-3

Grazing incidence X-ray diffraction (GID) was performed at the G2 station at Cornell
High Energy Synchrotron Source (CHESS) using a beam energy of 8.78 ± 0.01 keV (λ =
0.1414 nm), selected using a Be single-crystal monochromator. Motorized slits were used
to define a 0.2×2 (V×H) mm2 beam, with a typical flux of 2×1010 photons/s. The data
were collected using a 640-element 1D diode-array, of which each element incorporates
its own pulse counting electronics capable of count rates of ~105 photons/s. A set of 0.1°
Soller slits were used on the detector arm to define the in-plane resolution. The scattering
geometry is described in detail elsewhere.1 Each data set was collected by scanning the
detector with the sample stationary. The incidence angle α between the beam and sample
surface was 0.175°. Axes labels Q⊥ and Q|| are defined using the GISAXS convention Q⊥ =
4π/λsin(δ/2) and Q|| = 4π/λsin(ν/2), where δ and ν are the vertical and horizontal
scattering angles, respectively.2 At α=δ=0, hQ|| and hQ⊥ (where h is Planck’s constant) are
the components of momentum transfer parallel and perpendicular to the sample surface,
respectively.
S-4

B. Synthetic Procedures.
General procedure for COF powder synthesis and ZnPc-Py COF. Pyrene diboronic
acid 1 (17 mg, 0.059 mmol) and Zn octahydroxyphthalocyanine 5 (20 mg, 0.028 mmol)
were suspended in a mixture of dioxane and MeOH (2:1, 3 mL) and sonicated for 10 min.
The dark green suspension was transferred to a 10 mL pre-scored long-necked glass
ampoule, flash-frozen in liquid N2, and flame-sealed. The ampoule was placed in an
o
oven at 120 C for 72 h, and the resulting free-flowing dark green powder was collected
by filtration on a Hirsch funnel, washed with anhydrous toluene (1 mL), and air-dried.
The resulting ZnPc-Py COF powder (10 mg, 52%) was dried under vacuum before
characterization by PXRD and IR. ZnPc-Py COF: IR (powder, ATR) 3233, 1607, 1459,
1369, 1337, 1271, 1231, 1106, 1078, 1023, 902, 870, 824, 742, 714 cm-1. PXRD [2θ
(relative intensity)] 3.22 (100), 6.50 (24), 9.92 (5.6), 13.16 (4.3), 26.62 (6.4). UV-Vis
(powder, praying mantis DRA) 711, 377 (sh), 336, 284. Anal. Calcd. for
(C64H24B4N8O8Zn)n: C, 67.34; H, 2.12; N, 9.82. Found: C, 63.65; H, 2.20; N, 10.34. It has
been noted5,6 that elemental analysis of boronate COFs typically give lowered carbon
values from the formation of non-combustible boron carbide byproducts. The presence of
boron was confirmed by a characteristic B 1s peak in the XPS with a binding energy of
190.8 eV.
ZnPc-DPB COF. The above procedure was followed using diphenyl butadiynediboronic
acid 2 (17 mg, 0.059 mmol), Zn octahydroxyphthalocyanine 5 (14 mg, 0.020 mmol), and
a 3:1 mixture of dioxane and methanol (3:1, 1.3 mL) solvent. 12 mg (53%) of the ZnPc-
DPB COF were isolated. IR (powder, ATR) 3244, 1607, 1472, 1371, 1338, 1268, 1180,
1081, 1018, 869, 830, 742 cm-1. PXRD [2θ (relative intensity)] 2.66 (100), 3.74 (4.7),
5.45 (15), 8.29 (5.9), 11.04 (1.9), 13.82 (1.3), 16.48 (0.86), 26.83 (2.2). UV-Vis (powder,
praying mantis DRA) 713, 361 (sh), 301, 275 (sh). Anal. Calcd for (C64H24B4N8O8Zn)n:
C, 67.34; H, 2.12; N, 9.82. Found: C, 54.15; H, 2.19; N, 9.68. It has been noted5,6 that
elemental analysis of boronate COFs typically give lowered carbon values from the
formation of non-combustible boron carbide byproducts. The presence of boron was
confirmed by a characteristic B 1s peak in the XPS with a binding energy of 191.7 eV.
ZnPc-NDI COF. The above procedure was followed using napthalenediimide diboronic
acid 3 (36 mg, 0.071 mmol), Zn octahydroxyphthalocyanine 5 (17 mg, 0.024 mmol), and
S-5

a 2:1 mixture of dioxane and MeOH (3 mL) solvent. 23 mg (60%) of the ZnPc-NDI
COF were isolated. ZnPc-NDI COF: IR (powder, ATR) 3338, 1714, 1671, 1613, 1582,
1514, 1479, 1451, 1376, 1342, 1272, 1251, 1200, 1119, 1085, 1022, 984, 870, 835, 768,
742, 719 cm-1. PXRD [2θ (relative intensity)] 2.44 (100), 5.00 (27), 7.52 (7.0), 12.52
(3.3), 26.92 (2.6). UV-Vis (powder, praying mantis DRA) 693, 333 (sh), 296. Anal.
Calcd for (C84H32B4N12O16Zn)n: C, 64.10; H, 2.05; N, 10.68. Found: C, 55.41; H, 2.56; N,
11.09. It has been noted5,6 that elemental analysis of boronate COFs typically give
lowered carbon values from the formation of non-combustible boron carbide byproducts.
The presence of boron was confirmed by a characteristic B 1s peak in the XPS with a
binding energy of 191.3 eV.
ZnPc-PPE COF. The above procedure was followed using PPE diboronic acid 4 (22 mg,
0.060 mmol), Zn octahydroxyphthalocyanine 5 (15 mg, 0.021 mmol), and a 5:1 mixture
of dioxane and MeOH (3 mL) solvent. 20 mg (73%) of the ZnPc-PPE COF were
isolated. ZnPc-PPE COF: IR (powder, ATR) 3060, 2930, 1711, 1605, 1472, 1395, 1351,
1270, 1227, 1187, 1042, 1015, 945, 915, 872, 830, 745, 704 cm-1. PXRD [2θ (relative
intensity)] 2.28 (100), 4.76 (18), 7.20 (6.9), 9.68 (3.4), 12.16 (2.5), 26.52 (2.3). UV-Vis
(powder, praying mantis DRA) 693, 331, 308 nm. Anal. Calcd for (C84H32B4N12O16Zn)n:
C, 70.56; H, 2.49; N, 8.66. Found: C, 59.20; H, 2.58; N, 8.70. It has been noted5,6 that
elemental analysis of boronate COFs typically give lowered carbon values from the
formation of non-combustible boron carbide byproducts. The presence of boron was
confirmed by a characteristic B 1s peak in the XPS with a binding energy of 191.3 eV.
S-6

Scheme S1. Synthesis of naphthalene diimide diboronic acid 3.
N,N’-bis(4-iodophenyl)naphthalene-1,4,5,8-tetracarboxylic diimide (7). Naphthalene-
1,4,5,8-tetracarboxylic dianhydride 6 (1.30 g, 4.85 mmol) and 4-iodoaniline (3.20 g, 10.5
mmol) were refluxed in propionic acid (80 mL) for 18 h under N2. The brown solution
was cooled to rt and the resulting precipitate was collected by filtration and washed with
MeOH (4 x 20 mL). The resulting light brown solid 7 (2.40 g, 74%) was used without
further purification. Its poor solubility precluded acquisition of a suitable 13C-NMR
spectrum. 7: 1H-NMR (DMSO-d6, 300 MHz) δ 8.72 (s, 4H); 7.94 (d, J = 9 Hz, 4H); 7.30
(d, J = 9 Hz, 4H). MALDI-MS m/z (%) 542.9 (44, M+-I); 543.9 (52, M++1-I); 669.8 (100,
M+); 670.8 (53, M++1). IR (powder, ATR) 3100, 3068, 3049, 1711, 1670, 1577, 1484,
1446, 1344, 1248, 1198, 1118, 1006, 980, 884, 850, 827, 766, 741 cm-1. UV-Vis [λ /nm
(log ε / M-1 cm-1), 6.9 µM in DMF] 380 (4.43), 360 (4.43), 340 (4.34). Anal. Calcd for
(C26H12I2N2O4): C, 46.60; H, 1.80; N, 4.18. Found: C, 47.77; H, 1.84; N, 4.22.
Naphthalenediimide dipinacolatoboronic ester (8). Naphthalene diimide diiodide 7
(138 mg, 0.206 mmol) and nickel(II) diphenylphosphinopropane dichloride (9.0 mg,
0.017 mmol) were heated to reflux in toluene (2 mL) and N,N-diisopropylethylamine (1
mL) under N2. Pinacol borane (100 µL, 0.69 mmol) was added by syringe and the
mixture was stirred for 12 h. After cooling to rt, saturated aq. NH4Cl (30 mL) was added
to the dark brown mixture. The biphasic liquid was diluted with EtOAc (40 mL) and was
S-7

washed with H2O (3 x 40 mL). The organic layer was evaporated to provide a pale
yellow solid, which was suspended in EtOAc (10 mL) and centrifuged for 30 min at 4000
rpm. This suspension/centrifugation procedure was repeated twice. The tan solid 8 (73
1
mg, 53%) was dried under vacuum and used without further purification. 8: H-NMR
(CDCl3, 300 MHz) δ 8.84 (s, 4H); 8.04 (d, J = 9 Hz, 4H); 7.36 (d, J = 9 Hz, 4H); 1.38 (s,
24H). 13C-NMR (CDCl3, 300 MHz) δ 163, 138, 136, 132, 130, 128, 128, 127, 84, 25. IR
(powder, ATR) 3088, 2980, 2940, 1713, 1675, 1607, 1581, 1447, 1399, 1359, 1342,
1321, 1246, 1213, 1198, 1169, 1143, 1120, 1086, 1022, 983, 963, 860, 824, 794, 769, 717
cm-1. UV-Vis [λ /nm (log ε / M-1 cm-1), 8.1 µM in DMF] 380 (4.43), 360 (4.42), 343
(4.25). Anal. Calcd for (C38H36B2N2O8): C, 68.09; H, 5.41; N, 4.18. Found: C, 68.05; H,
5.39; N, 4.28.
Naphthalenediimide diboronic acid (3). Ester 8 (30 mg, 0.045 mmol) and NaIO4 (20
mg, 0.094 mmol) were suspended in a 4:1 THF:H2O solution (0.6 mL). The resulting tan
mixture was stirred for 2 h, after which aq. HCl (1M, 1 mL) was added. The pale yellow
suspension was stirred for 18 h and diluted with H2O (5 mL), filtered, and rinsed with
another 5 mL H2O. The resulting tan solid was dried under vacuum to provide the
1
diboronic acid 3 (16 mg, 70 %). 3: H-NMR (DMSO-d6, 300 MHz) δ 8.72 (s, 4H); 8.23
(s, 4H); 7.94 (d, J = 6 Hz, 4H); 7.42 (d, J = 6 Hz, 4H). 13C-NMR (DMSO-d6, 300 MHz)
δ 164, 138, 135, 131, 130, 129, 128, 127. IR (powder, ATR) 3479, 3378, 1711, 1664,
1606, 1577, 1437, 1416, 1366, 1341, 1275, 1250, 1199, 1151, 1127, 1061, 1028, 1015,
984, 890, 854, 828, 767, 752, 719 cm-1. UV-Vis [λ /nm (log ε / M-1 cm-1), 15.0 µM in
DMF] 380 (4.40), 360 (4.38), 345(sh) (4.21). Anal. Calcd for (C26H16B2N2O8): C, 61.71;
H, 3.19; N, 5.54.Found: C, 62.31; H, 3.21; N, 5.39.
S-8

Scheme S2. Synthesis of phenylbis(phenylethynyl)diboronic acid 4.
Benzene-1,4-bis(phenylethynyl) diboronic acid (4). 4-iodophenylboronic acid (880 mg,
3.55 mmol) and 1,4-diethynylbenzene (205 mg, 1.63 mmol) were dissolved in THF (25
mL) and ethyldiisopropylamine (10 mL) and the solution was sparged with N2 for 30
min. CuI (63 mg, 0.33 mmol) and Pd(PPh3)4 (43 mg, 0.037 mmol) were added and the
solution was sparged with N2 for another 30 min. The resulting pale yellow mixture was
stirred at rt for 12 h, during which a white precipitate formed. The pale yellow solid was
recovered by filtration and rinsed with EtOAc (20 mL). The solid was suspended in
EtOAc (30 mL), which washed with brine (30 mL) and H2O (3 × 30 mL), and the solvent
removed to yield 513 mg (86%) of the PPE diboronic acid 4 as a white solid. 4: 1H-NMR
(DMSO-d6, 300 MHz) δ 8.20 (s, 4H); 7.84 (d, J = 7.5 Hz, 4H); 7.60 (d, J = 3 Hz, 4H);
13
7.54 (d, J = 7.5 Hz, 4H). C-NMR (DMSO-d6, 300 MHz) δ 135, 133, 130, 123, 122,
92,90. MALDI-MS m/z (%) 365.1 (43, M+); 366.1 (100, M++1); 367.1 (27, M++2), 368.1
(6, M++3). IR (powder, ATR) 3351, 1701, 1658, 1592, 1576, 1505, 1491, 1434, 1401,
1358, 1256, 1199, 1183, 1143, 1088, 1021, 957, 857, 831, 808, 743, 693 cm-1. UV-Vis [λ
/nm (log ε / M-1 cm-1), 9.4 µM in DMF] 350 (4.63), 329 (4.83), 321(sh) (4.75). Em (λ/nm
in DMF, λex = 350 nm) 376, 387, 400(sh). Anal. Calcd for (C22H16B2O4): C, 72.20; H,
4.41. Found: C, 69.62; H, 4.37.
S-9

Graphene Growth. Single-layer graphene was grown on 25 µm-thick copper foil using
previously reported chemical vapor deposition methods.7 A layer of PMMA (50 nm) was
spin-coated on top of the graphene and the copper was etched using aq. FeCl3. The
graphene was then transferred to fused SiO2 and the PMMA removed by washing first
with chloroform then isopropyl alcohol. The SLG/SiO2 was finally calcined at 300 °C for
2.5 h.
General procedure for ZnPc COF film growth on SLG. The appropriate diboronic
acid (0.109 mmol) and zinc octahydroxyphthalocyanine (0.035 g, 0.050 mmol) were
added to a 15 mL cylindrical pressure vessel and suspended in a mixture of 1,4-dioxane,
methanol, N,N-dimethylacetamide, and 1,2-dichlorobenzene (v/v 3:1:2:1; 3.0 mL). After
capping, the mixture was sonicated for 30 minutes and a graphene-containing substrate
was added. The sealed vessel was heated in a 120 °C oven for 24 h. The vessel was
cooled to room temperature and the resulting green powder was recovered by filtration
and dried under vacuum. The graphene-containing substrate was submerged in anhydrous
toluene and sonicated for 5 seconds, and finally dried under vacuum.
S-10

C. NMR Spectra.
Figure S1. 1H-NMR spectrum of NDI diiodide 7 in DMSO-d6.
S-11

Figure S2. 1H-NMR spectrum of NDI ester 8 in CDCl3.
Figure S3. 13C-NMR spectrum of NDI ester 8 in CDCl3.
S-12

Figure S4. 1H-NMR spectrum of NDI diboronic acid 3 in DMSO-d6.
Figure S5. 13C-NMR spectrum of NDI diboronic acid 3 in DMSO-d6.
S-13

Figure S6. 1H-NMR spectrum of PPE diboronic acid 4 in DMSO-d6.
Figure S7. 13C-NMR spectrum of PPE diboronic acid 4 in DMSO-d6.
S-14

D. FT-IR Spectra.
Figure S8. FT-IR of pyrene diboronic acid 1 (blue) and ZnPc-Py COF (red).
100
90
80
70
60
3700
3200
2700
2200
(cm )
1700
1200
700
-1
ν
Figure S9. Expansion of 700-1800 cm-1 region of the above spectrum.
100
90
80
70
60
1700
1500
1300
1100
900
700
-1
ν
(cm )
S-15

Figure S10. FT-IR of DPB acid 2 (blue) and ZnPc-DPB COF (red).
100
90
80
70
60
50
3700
3200
2700
2200
1700
1200
700
-1
ν
(cm )
Figure S11. Expansion of 700-1800 cm-1 region of the above spectrum.
100
90
80
70
60
50
1700
1500
1300
1100
900
700
-1
ν
(cm )
S-16

Figure S12. FT-IR of NDI diiodide 7 (blue) and pinacolboronate ester 8 (red).
100
90
80
70
60
3700
3200
2700
2200
1700
1200
700
-1
ν
(cm )
Figure S13. Expansion of 700-1800 cm-1 region of the above spectrum.
100
90
80
70
60
1700
1500
1300
1100
900
700
-1
ν
(cm )
S-17

Figure S14. FT-IR of NDI acid 3 (blue) and ZnPc-NDI COF (red).
100
95
90
85
80
75
70
3700
3200
2700
2200
1700
1200
700
-1
ν
(cm )
Figure S15. Expansion of 700-1800 cm-1 region of the above spectrum.
100
95
90
85
80
75
70
1700
1500
1300
1100
900
700
-1
ν
(cm )
S-18

Figure S16. FT-IR of diboronic acid 4 (blue) and ZnPc-PPE COF (red).
100
90
80
70
60
50
40
30
3700
3200
2700
2200
(cm )
1700
1200
700
-1
ν
Figure S17. Expansion of 700-1800 cm-1 region of the above spectrum.
100
90
80
70
60
50
40
30
1700
1500
1300
1100
900
700
-1
ν
(cm )
S-19

E. UV-Vis-NIR Characterization
Figure S18. Diffuse reflectance absorption spectra of ZnPc-Py COF (gold), ZnPc-DPB
COF (blue), ZnPc-NDI COF (red) and ZnPc-PPE COF (purple) powders.
S-20

F. Simulation & Refinement of the COF Structures. Crystal modeling of the COFs
was carried out using the Materials Studio (ver.5.0) suite of programs by Accelrys.8 The
initial structures were constructed piecewise starting with a primitive tetragonal unit cell
with space group P4/mmm. The a cell parameter was estimated according to the distance
between the center of the vertices for each COF as shown in Figure S19, and c parameter
was arbitrarily chosen as 3.35 Å. The structures were optimized using the Geometry
Optimization routine including energy minimization with cell parameters optimization,
using the parameters from the Universal Force Field. Modeling of the staggered
structures was performed in a similar manner but starting with the space group I4/mmm,
and c = 6.70 Å. Calculation of the simulated powder diffraction patterns and Pawley
refinements were performed the Materials Studio Reflex Plus Module. The observed
diffraction patterns were subjected to Pawley refinement wherein peak profile were
refined using the Pseudo-Voigt peak shape function and asymmetry was corrected using
the Berar-Baldinozzi function.5
S-21

Figure S19. Precursor structures used for initial modeling of the COF structures.
ZnPc-Py Monomer
ZnPc-DPB Monomer
S-22

Figure S20. Modeled COF crystals.
ZnPc-Py COF
ZnPc-NDI COF
ZnPc-DPB COF
ZnPc-PPE COF
S-23

Figure S21. Observed (blue) versus Pawley-refined (red) PXRD pattern profiles for
ZnPc-Py COF. Residuals are indicated.
Observed Profile
Refined Profile
Rwp = 6.83%
Rp = 5.57%
0
10
20
30
θ
2 (Degree)
Figure S22. Observed (blue) versus Pawley-refined (red) PXRD pattern profiles for
ZnPc-DPB COF. Residuals are indicated.
Observed Profile
Refined Profile
Rwp = 5.32%
Rp = 3.93%
0
10
20
30
θ
2 (Degree)
S-24

Figure S23. Observed (blue) versus Pawley-refined (red) PXRD pattern profiles for
ZnPc-NDI COF. Residuals are indicated.
Observed Profile
Refined Profile
Rwp = 7.48%
Rp = 5.31%
0
10
20
30
θ
2 (Degree)
Figure S24. Observed (blue) versus Pawley-refined (red) PXRD pattern profiles for
ZnPc-PPE COF. Residuals are indicated.
Observed Profile
Refined Profile
Rwp = 8.30%
Rp = 6.43%
0
10
20
30
θ
2 (Degree)
S-25

Table S1. Comparison of unit cell parameters of the simulated crystals, the d-spacing of
the 100 diffraction peaks and the refined patterns for each prepared COF.
ZnPc-Py COF
MS modeling
d100
a (Å)
c (Å)
3.535
27.185
27.056
26.980
Pawley refinement
3.338
ZnPc-DPB COF
MS modeling
d100
a (Å)
c (Å)
3.556
32.469
33.060
32.183
Pawley refinement
3.356
ZnPc-NDI COF
MS modeling
d100
a (Å)
c (Å)
3.542
36.064
36.176
35.701
Pawley refinement
3.361
ZnPc-PPE COF
MS modeling
d100
a (Å)
c (Å)
3.552
36.718
37.403
38.533
Pawley refinement
3.367
S-26

Table S2. Fractional atomic coordinates for refined unit cell of ZnPc-Py COF.
Tetragonal,
(P4/mmm)
a = b = 26.980 Å, c = 3.338 Å
atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
O1
B1
x
y
z
0.027462
0.027462
0.053706
0.105674
0.131288
0.265000
0.309000
0.355000
0.401000
0.212025
0.182823
0.430000
0.416000
0.500000
0.500000
0.410860
0.455430
0.455430
0.500000
0.475000
0.450000
0.475000
0.462000
0.546591
0.500000
0.500000
0.584000
0.500000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
N1
N2
Zn1
Table S3. Fractional atomic coordinates for refined unit cell of ZnPc-DPB COF.
Tetragonal
(P4/mmm)
a = b = 32.183 Å, c = 3.356 Å
atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
O1
B1
x
y
z
0.020491
0.057698
0.102075
0.123748
0.166807
0.188528
0.300642
0.337406
0.373823
0.414478
0.261315
0.236652
0.440321
0.428054
0.500000
0.500000
0.500000
0.500000
0.464739
0.464739
0.500000
0.480551
0.457860
0.480551
0.469042
0.464137
0.500000
0.500000
0.428054
0.500000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
N1
N2
Zn1
S-27

Table S4. Fractional atomic coordinates for unit cell of ZnPc-NDI COF calculated using
the Materials Studio ver.5.0 modeling program.
Tetragonal
(P4/mmm)
a = b = 35.701 Å, c = 3.361 Å
atom
C1
C2
C3
C4
C5
C6
C7
C8
x
y
z
0.019879
0.019879
0.039699
0.079187
0.140886
0.162059
0.201335
0.221662
0.319419
0.352942
0.386323
0.423494
0.095827
0.285292
0.263921
0.099281
0.447162
0.434520
0.500000
0.500000
0.433099
0.466552
0.466552
0.500000
0.466552
0.466552
0.500000
0.480860
0.460236
0.480974
0.470264
0.435714
0.467504
0.500000
0.500000
0.500000
0.434520
0.500000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
C9
C10
C11
C12
O1
O2
B1
N1
N2
N3
Zn1
Table S5. Fractional atomic coordinates for unit cell of ZnPc-PPE COF calculated using
the Materials Studio ver.5.0 modeling program.
Tetragonal
(P4/mmm)
a = b = 38.533 Å, c = 3.367 Å
atom
C1
C2
C3
C4
C5
C6
C7
C8
x
y
z
0.018677
0.038444
0.078109
0.110866
0.150530
0.170299
0.207616
0.227438
0.327400
0.359425
0.391299
0.426676
0.293260
0.270958
0.437864
0.448380
0.500000
0.468853
0.500000
0.500000
0.500000
0.500000
0.468853
0.468853
0.500000
0.481973
0.462877
0.482008
0.471666
0.468194
0.500000
0.437864
0.500000
0.500000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
C9
C10
C11
C12
O1
B1
N1
N2
Zn1
S-28

Figure S25. Crystal models of ZnPc-Py COF (top left), ZnPc-DPB COF (top right),
ZnPc-NDI COF (bottom left) and ZnPc-PPE COF (bottom right) in a staggered
conformation and corresponding simulated PXRD patterns. Similarly colored sheets are
in alternating unit cells. Note the lack of match to observed PXRD patterns (vide supra).
S-29