Molecules 2019, 24, 3361
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solvent as standard. Solid-state 13C CP/MAS NMR measurements were measured on Bruker AVANCE
III HD at a MAS rate of 5 kHz and a CP contact time of 2 ms.
3
.2. General Materials and Methods
Pyrrol, p-nitrobenzaldehyde, phosphorus oxychloride, N-alkyl carbazole were obtained from
Aladdin. Propionic acid, acetic anhydride, conc. HCl, SnCl2
Sinopharm Chemical Reagent Limited Company. Pyridine, THF, n-hexane, dimethylformamide,
,2-dichloroethane, chloroform, Tianjin Fuyu Fine Chemical Limited Company. All other reagents and
·
2H O, NH3
·
H O were obtained from
2
2
1
solvents were commercially available and used as purchased without further purification. Soxhlet
extraction was conducted through Soxhlet apparatus with THF.
Molecular modeling and Pawley refinement were implemented using Reflex, a module in Materials
Studio 7. Unit cell parameters were first manually calculated from the observed PXRD peak positions
using the Bragg equation. We utilized Pawley refinement to optimize the lattice parameters iteratively
until the Rwp value converges. The pseudo-Voigt profile function was used for whole profile fitting
and Berrar–Baldinozzi function was used for asymmetry correction during the refinement processes.
The final Rwp and Rp values were Rwp = 1.97% and Rp = 1.02%.
0
3
.3. Synthesis of 5,10,15,20-Tetrakis(4 -Nitrophenyl)Porphyrin
A 250-mL three-neck round bottom flask was contained the mixture of propionic acid (110 mL)
◦
and acetic anhydride (5 mL), p-nitrobenzaldehyde (1.4 g, 9.27 mmol) was heated to 173 C, then freshly
distilled pyrrole (0.64 mL, 9.27 mmol) was added dropwise. After dropping, the solution was stirred
◦
at 173 C for 1 h. After the reaction completed, the dark violet precipitate was collected by filtration
and washed with methanol. The crude product was dissolved in 100 mL pyridine and refluxed with
stirring for 4 h, after cooling to room temperature, the product was collected by filtration to give
0
5
,10,15,20-tetrakis(4 -nitrophenyl) porphyrin as violet powder (0.98 g) in 13% yield. The product was
1
used directly for the next step without further purification. H NMR (CDCl , 300 MHz):
δ
(ppm)–2.80(s,
3
2
H, NH), 8.33 (d, 8H aromatics), 8.606 (d, 8H, aromatics), 8.755 (s, 8H, H-pyrrole).
0
3
.4. Synthesis of 5,10,15,20-Tetrakis(4 -Aminophenyl)Porphyrin
0
The compound was prepared according to the literature. [43] A mixture of 5,10,15,20-tetrakis(4 -
◦
nitrophenyl)porphyrin (1.2 g, 1.5 mmol) in concentrated HCl (75 mL) was heated up to 70 C, to which
◦
SnCl
0
·
2H O (9 g, 40 mmol) was added. The mixture was stirred at 70 C for 30 min and then cooled to
C. Aqueous NH was added slowly to neutralize HCl, the precipitate was collected by filtration
3
2
2
◦
and dissolved in THF. Then the solution was collected by filtration and recrystallized with n-hexane,
0
1
to give 5,10,15,20-tetrakis(4 -aminophenyl)porphyrin as violet crystal (408 mg) in 40% yield. H NMR
DMSO-d , 300 MHz): (ppm)–2.731 (s, 2H, NH), 5.541 (s, 8H, NH ), 7.013 (d, 8H, aromatics), 7.858 (d,
(
δ
6
2
8
H, aromatics), 8.874 (s, 8H, H-pyrrole).
3
.5. Synthesis of 3,6-Diformyl-9-Ethylcarbazole
The compound was prepared according to the literature. [44] A 250-mL three-neck round bottom
◦
flask was contained dimethylformamide (DMF, 11 g, 0.15 mol) and cooled to 0 C. Phosphorus
oxychloride (23 g, 0.15 mol) was added dropwise. The solution was allowed to warm up to room
temperature and stirred for 1 h, and added a solution of N-ethyl carbazole (2.93 g, 0.015 mol) in 40 mL
◦
1
,2-dichloroethane. Then the solution was heated to 90 C for 48 h. After the reaction completed,
it was slowly poured into ice water, and extracted with chloroform for three times. The solution was
evaporated under vacuum and the crude product was purified by column chromatography (silica
1
gel, 99:1 v/v dichloromethane/methanol) provided a white solid (1.8g) in 61% yield. H NMR (CDCl ,
3
300 MHz):
δ(ppm) 1.522 (t, 3H, CH ), 4.485 (q, 2H, CH ), 7.758 (d, 2H, carbazole), 8.115 (d, 2H,
3 2
carbazole), 8.683 (s, 2H, carbazole), 10.145 (s, 1H, CH=O).