SUPPLEMENTARY INFORMATION
Design and synthesis of nanoporous perylene bis-imide linked
metalloporphyrin frameworks and their catalytic activity
MANOJ KUMAR SINGH and DEBKUMAR BANDYOPADHYAY*
Department of Chemistry, Indian Institute of Technology Delhi, HauzKhas, New Delhi 110 016,
India
e-mail: dkbp@chemistry.iitd.ac.in
*for Correspondence
Section 1. Materials and synthesis
Section 2. FT IR Spectroscopy
Section 3. EDX (Energy dispersive X-ray spectroscopy)
Section 4. Magnetic Suscepetibility measurements
Section 5. Powder X-ray diffraction
Section 6. Pore size measurement and distribution by NLDFT
Section 7. Recyclability of the catalyst
Section 8. Supporting references
S-1
Section 1.Materials and Synthesis
m-Cresol was distilled under Ar before use. Other organic solvents for reactions were
distilled over appropriate drying reagents under argon or obtained as dehydrated reagents from
Merck (India)Chemicals. Deuterated solvents for NMR, pyrrole, p-nitrobenzaldehyde, tert-butyl
hydroperoxide (t-BuOOH) and perylen-3,4,9,10-tetracarboxylic dianhydride were obtained from
Sigma-Aldrich Chemical Pvt. Ltd (U.S.A.). Ferrous chloride tetrahydrate and manganous acetate
tetrahydrate were obtained from LobaChemie. SnCl2.2H2O, acetic anhydride and hydrochloric
acid obtained from Qualigens Chemicals. Isoquinoline, ethanol and m-cresol were obtained from
Spectrochemicals. Olefines were obtained from Sigma-Aldrich.
Synthesis of 5,10,15,20-Tetrakis(4’-nitrophenyl)porphyrin[S1]
A solution of p-nitrobenzaldehyde (1.4 g, 9.27 mmol) in propionic acid (110 mL) and
acetic anhydride (5 mL) was heated up to 173°C, and added with freshly distilled pyrrol (0.64
mL, 9.27mmol). The reaction mixture was stirred at 173°C for 4 h under argon atmosphere,
cooled to room temperature. The resulted dark violet precipitate was collected by filtration and
washed with methanol (50 mL x3). The powdery solid obtained was then taken in 25 mL of
pyridine and refluxed with stirring for 4 h, cooled to room temperature and stored at -4ºC for 24
h. The tarry mixture was filtered and the solid product was washed with acetone until the
washings were not dark. The product was further purified by silica gel column chromatography
by using 6% methanol in dichloromethane, to give 5,10,15,20-Tetrakis(4’-nitrophenyl)porphyrin
as violet crystalline powder (1.2 g) in 16% yield. 1H NMR (CDCl3, 300 MHz): δ (ppm) –2.80(s,
2H, NH), 8.33 (d, 8H, J = 8.3 Hz, aromatics), 8.606 (d, 8H, J = 8.3 Hz, aromatics), 8.755 (s, 8H,
H-pyrrole). ESI-MS: m/z calcd for C44H34N8O8, 795.1952 [M+H]+; found, 795.1946 [M+H]+.
UV-Vis (λ; nm; CH2Cl2 solution): 380, 424, 516, 552, 592 and 647.
Synthesis of 5,10,15,20-Tetrakis(4’-aminophenyl)porphyrin[S2]
A solution of 5,10,15,20-Tetrakis(4’-nitrophenyl)porphyrin (1.2 g, 1.5 mmol) in conc.
HCl (75 mL) was heated up to 70°C under argon atmosphere for 1 h, and added a solution of
SnCl2.2H2O (9 g, 40mmol) in 140 mL of conc. HCl. The reaction mixture was stirred at 70°C for
16 h under argon atmosphere, cooled to room temperature and neutralized by slow addition of
liquor ammonia, carefully maintaining the low temperature of exothermic reaction. The resulted
greenish precipitate was collected by filtration and was vigorously stirred in 5% NaOH solution
for 2 h. the solid residue was filtered, washed with water, dried and then extracted by soxhlet
extractor using 250 mL of chloroform. The volume of the chloroform solution was then reduced
to 150 mL by rotary evaporation and 200 mL of 5% ethanol was added into it. The solvent was
removed by rotary evaporation and solid 5,10,15,20-Tetrakis(4’-aminophenyl)porphyrin was
S-2
collected and further purified by silica gel column chromatography using 9 % methanol in
dichloromethane, to give 5,10,15,20-Tetrakis(4’-aminophenyl)porphyrin as violet crystalline
powder (245 mg) in 24% yield. 1H NMR (CDCl3, 300 MHz): δ (ppm) –2.689(s, 2H, NH), 4.045
(s, 8H, NH2), 7.087 (d, 8H, J = 8.3 Hz, aromatics), 8.012 (d, 8H, J = 8.3 Hz, aromatics), 8.916 (s,
8H, H-pyrrole). ESI-MS: m/z calcd for C44H34N8, 675.2985 [M+H]+; found, 675.2966 [M+H]+.
UV-Vis (λ; nm; CHCl3 solution): 345, 428, 522, 563, and 657.
Synthesis of Iron(III)
NH2] 4PFeCl)[S3]
5,10,15,20-Tetrakis-(4’-aminophenyl)porphyrin
chloride
([p-
5,10,15,20-Tetrakis(4’-aminophenyl)porphyrin (100 mg, 0.148mmol) and FeCl2.4H2O
(300mg, 1.5mmol) were placed into a 250-mL flask and was added with a degassed DMF (100
mL) under argon. 100 µL (0.756 mmol) of collidine was added to the refluxing mixture and
solution was refluxed gently. After 1 h, second batch of FeCl2.2H2O (300 mg, 1.5 mmol) was
dissolved in 5 mL of previously degassed DMF and added to the reaction mixture. Then the
reaction mixture was carried on for another 3 h, cooled to room temperature and dropwise added
with an aqueous hydrochloric acid solution (3.0 M, 20 mL). The resulted precipitate was filtered
and washed with an aqueoushydrochloricacid solution (3.0 M, 20 mL) and H2O (200 mL x2).
The crude product was further purified by recrystallization from chloroform and methanol twice
to give [p-NH2]4PFe (95 mg, 0.124 mmol) as brown-red powder in 84% yield. ESI-MS: m/zcalcd
for C44H32ClFeN8, 728.2099 [M-Cl]+; found 728.2067 [M-Cl]+. FT IR (ν; cm–1): 3436, 1726,
1635, 1605, 1516, 1465, 1286, 1124, 1019 (δFe–N), 805 and 742. UV-Vis (λ; nm; CH2Cl2
solution): 385, 427, 516 and 707.
Synthesis of manganese(III) 5,10,15,20-Tetrakis-(4’-aminoophenyl)porphyrin chloride ([pNH2] 4PMnCl)[S4]
5,10,15,20-Tetrakis(4’-aminophenyl)porphyrin
(100
mg,
0.148mmol)
and
Mn(OAc)2.4H2O (500mg, 7.54 mmol) were placed into a 250-mL flask and dried in vacuum for
2 h and was added with a degassed DMF (100 mL) under argon. The mixture was stirred at 150
°C for 2 h, cooled to room temperature and dropwise added with an aqueous hydrochloricacid
solution (3.0 M, 20 mL). The resulted precipitate was filtered and washed with an aqueous
hydrochloric acid solution (3.0 M, 20 mL) and H2O (200 mLx2). The crude product was further
purified by recrystallization from chloroform and methanol twice to give [p-NH2]4PMn (248 mg,
0.24 mmol) as brown-red powder in 75% yield. ESI-MS: m/z calcd for C44H32ClMnN8,
727.2124; found 727.2113. FT IR (ν; cm–1): 3438, 1727, 1637, 1604, 1518, 1466, 1286, 1125,
1020 (δMn–N), 805 and 744. UV-Vis (λ; nm; CH2Cl2 solution): 382, 475, 633 and 660.
S-3
Table S1. Solubility
manganese(III)porphyrin
and
stability
of
perylenebis-imide
linked
iron(III)
Media
Solubility
Stability
Dichloromethane
Insoluble
Stable
Acetonitrile
Insoluble
Stable
Toluene
Insoluble
Stable
THF
Insoluble
Stable
Methanol
Insoluble
Stable
Acetone
Insoluble
Stable
m-Cresol
Insoluble
Stable
DMSO
Insoluble
Stable
Hexane
Insoluble
Stable
Water
Insoluble
Stable
Air
-
Stable
&
Solubility and stability of the polymer was tested at room temperature for the
corresponding media for one month.
S-4
Section 2. FT IR spectroscopy
Fig. S1:FT-IR spectra of perylenebis-imide linked iron(III)porphyrin (Black curve) and
perylenebis-imide linked manganese(III)porphyrin (Red curve). The dotted line around 1020 cm–
1
& 1020cm–1indicates the vibration band due to N–Fe bond andN–Mn respectively, while peaks
at 3118(w) & 3119(w) cm–1originate from C–H stretching of the perylene moiety in the
respective sample.
Table S2.Assignment of FT-IR peaks of perylenebis-imide linked iron(III)porphyrin
Peak (cm-1)
3118
1769
1698
1658
1588
1504
1401
1350
1299
1237
1124(m)
1020
858
803
736
Assignment and notes
Perylene moiety C-H stretching
Imide asymmetrical –C=O
Imide symmetrical –C=O
C=O stretching
C=C stretching of the pyrrole rings
C=C vibrational mode of phenyl rings
Imide ring stretching
C-N stretching
C-H in plane bending mode of phenyl rings
Pyrrole stretching
Fe-N Stretching
C-H perylene wag
C-H out of plane bending of phenyl rings
S-5
Table S3.Assignment of FT-IR peaks of perylenebis-imide linked manganese(III)porphyrin
Peak (cm-1)
3119
1770
1699
1660
1589
1502
1404
1351
1300
1234
1124(m)
1020
860
803
732
Assignment and notes
Aromatic C-H stretching frequency
Imide asymmetrical –C=O
Imide symmetrical –C=O
C=C stretching frequency
C=C stretching of the pyrrole rings
C=C vibrational mode of phenyl rings
Imide ring stretching
C-N stretching
C-H in plane bending mode of phenyl rings
Pyrrole stretching
Mn-N Stretching frequency
C-H perylene wag
C-H out of plane bending of phenyl rings
S-6
Section 3. EDX spectroscopy
cps/eV
Object 554
16
14
12
10
Cl N
C O Fe
Si
Cl
Fe
8
6
4
2
0
0
1
2
3
4
keV
5
6
7
8
9
Fig. S2: EDX measurement for perylenebis-imide linked iron(III)porphyrin
cps/eV
Object 551
16
14
12
10
Cl Sn Mn
C O
Na
Cl
Sn Ca
Mn
Ca
8
6
4
2
0
0
1
2
3
4
keV
5
6
7
Fig. S3: EDX measurement for perylenebis-imide linked manganese(III)porphyrin
S-7
8
9
Section 4: Magnetic susceptibility measurements (5 K to 300K then 300K to 5K).
Fig. S4:Magnetic susceptibility measurement for perylene linked bis-imide iron(III) porphyrin.
Fig. S5: Magnetic susceptibility measurement for perylenelinked bis-imide manganese(III)
porphyrin.
S-8
Section 5.PXRD (Powder X-Ray Diffraction)
Fig. S6. PXRD pattern of Perylenebis-imide linked Fe(III)porphyrin COF
Fig. S7. PXRD pattern of Perylenebis-imide linked Mn(III)porphyrin COF
S-9
Section 6.Pore size measurement and distribution by NLDFT
Fig. S8: Pore size distribution of perylene linked bisimidemetalloporphyrins by NLDFT
modeling on the N2 adsorption isotherm.
S-10
Section 7.Recyclability of the catalyst
TableS4: Recyclability of the perylenebisimide linked iron(III)porphyrin catalyst for oxidation
of norbornene with t-BuOOH
Entry
1
2
3
4
5
6
7
8
9
10
Total conc. of
oxidant
(mM)
10
20
30
40
50
60
70
80
90
100
Time
(hrs)
No. of
recycle
8
8
8
8
8
8
8
8
8
8
1
2
3
4
5
6
7
8
9
10
Conversion(%) Selectivity(%)
99
99
99
99
99
99
99
99
99
99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
Norbornene (400mM), Oxidant (10mM) per cycle, Catalyst (3.16 µmol), Dichloromethane
(2mL), stirred at room temperature under argon atmosphere. The yields are w.r.t. oxidant.
Section 8. Supporting references
[S1] A. D. Adler, F. R. Longo, J. D. Finarelli, J. Assour, L. Korsakoff, J. Org. Chem.,1967, 32,
476.
[S2] R. Luguya, L. Jaquinod, F. R. Fronczek, M. G. H. Vicente, K. M. Smith, Tetrahedron,
2004, 60, 2757.
[S3] E. B. Fleischer, J. M. Palmer, T. S. Srivastava, A. Chatterjee, J. Am. Chem. Soc., 1971, 93,
3162.
[S4]A. D. Adler, F. R. Longo,F.Kampes, J. Kim,J. Inorg. Nucl.Chem., 1970, 32, 2443.
S-11