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Chemical Structure| 14609-54-2

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Synonyms: TCPP

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Ahmad, Mohammad Shahwaz ; Samokhvalov, Alexander ;

Abstract: Metal-organic frameworks (MOFs) are 3-dimensional coordination polymers which contain metals and organic linkers. MOFs are of strong interest in the fields of separation, catalysis, chemo-sensing, and pollution remediation. MOFs are highly desired, which have complex and controlled composition, structure and functional properties. Here, we report the copper porphyrin aluminum MOF (actAl-MOF-TCPPCu) denoted compound 4, and mechanistic and kinetic studies of adsorption of volatile organic sulfur compound, diethyl sulfide (DES) by it. The characterization is conducted by qualitative and quantitative methods, structural analysis with the Rietveld crystal lattice refinement, and complementary microscopy and spectroscopy. Then a comprehensive study of mechanism and kinetics of DES sorption is presented, under the dynamic conditions in the flow of air. The latter is conducted by a novel method of in-situ time-dependent ATR-FTIR spectroscopy in the controlled environment. The binding sites of DES include the µ(O–H), the COO group, phenyl and pyrrole groups and they are ranked by the strengths of bonding. The kinetics of sorption obeys the Langmuir model of the pseudo-first order rate law with effective rate constant keff = 0.95±0.05 min−1. Moreover, the linear dependence of kinetic rate constant on concentration of DES suggests that the sorption is diffusion limited. The sorption of DES in the static equilibrium conditions results in the binary stochiometric adsorption complex with formula (Al-MOF-TCPPCu)2(DES)7. Finally, a facile regeneration of the adsorption complex was achieved, without using chemicals. The copper-containing porphyrin aluminum MOF and related materials are promising for the removal of volatile organic sulfur compounds from air.

Keywords: Metal-organic framework ; Sorption ; Diethyl sulfide ; ATR-FTIR spectroscopy ; Controlled atmosphere ; In-situ ; Time-dependent ; Kinetics

Purchased from AmBeed:

Ahmad, Mohammad Shahwaz ; Samokhvalov, Alexander ;

Abstract: Metal-organic frameworks (MOFs) are hybrid inorganic-organic 3D coordination polymers with metal sites and organic linkers, which are a “hot” topic in the research of sorption, separations, catalysis, sensing, and environmental remediation. In this study, we explore the molecular mechanism and kinetics of interaction of the new copper porphyrin aluminum metal-organic framework (actAlMOF-TCPPCu) compound 4 with a vapor of the volatile organic sulfur compound (VOSC) diethyl sulfide (DES). First, compound 4 was synthesized by post-synthetic modification (PSM) of AlMOF-TCPPH2 compound 2 by inserting Cu2+ ions into the porphyrin ring and characterized by complementary qualitative and quantitative chemical, structural, and spectroscopic analysis. Second, the interaction of compound 4 with DES vapor was analyzed dynamically by the novel method of in situ time-dependent attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy at controlled humidity levels. The sorbent-adsorbate interactions, as analyzed by the shifts in IR peaks, indicate that the bonding includes the hydroxy O-H, carboxylate COO, and phenyl groups. The kinetics of sorption obeys the Langmuir pseudo-first-order rate law. The pre-adsorption of water vapor by compound 4 at the controlled relative humidity under static (equilibrium) conditions yields the binary stoichiometric adsorption complex (Al-MOF-TCPPCu)1.0(H2O)8.0. The pre-adsorption of water vapor makes the subsequent sorption of DES slower, while the kinetics obey the same rate law. Then, static pre-adsorption of water vapor was followed by static sorption of DES vapor, and the ternary adsorption complex (Al-MOF-TCPPCu)1.0(H2O)8.0(DES)3.8 was obtained. Despite the pre-adsorption of significant amounts of water, the binary complex adsorbs a large amount of DES: ca. 36.6 wt. % (per compound 4). Finally, the ternary complex is facilely regenerated by gentle heating under vacuum. Compound 4 and related MOFs are promising for adsorptive removal of vapor of DES and related VOSCs from dry and humid air

Keywords: MOF ; metallo-porphyrin ; diethyl sulfide ; adsorption ; water ; controlled atmosphere ; ATR-FTIR ; in situ ; XRD ; Langmuir kinetics

Purchased from AmBeed: ;

Alternative Products

Product Details of Tetrakis (4-carboxyphenyl) porphyrin

CAS No. :14609-54-2
Formula : C48H30N4O8
M.W : 790.77
SMILES Code : O=C(O)C1=CC=C(C2=C3C=CC(C(C4=CC=C(C=C4)C(O)=O)=C5C=CC(N5)=C(C6=CC=C(C=C6)C(O)=O)C(C=C7)=NC7=C(C8=CC=C(C=C8)C(O)=O)C9=CC=C2N9)=N3)C=C1
Synonyms :
TCPP
MDL No. :MFCD00064860
InChI Key :HHDUMDVQUCBCEY-UHFFFAOYSA-N
Pubchem ID :86278368

Safety of Tetrakis (4-carboxyphenyl) porphyrin

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of Tetrakis (4-carboxyphenyl) porphyrin

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 14609-54-2 ]

[ 14609-54-2 ] Synthesis Path-Downstream   1~5

  • 1
  • [ 67-56-1 ]
  • [ 14609-54-2 ]
  • [ 22112-83-0 ]
YieldReaction ConditionsOperation in experiment
at 169.84℃; for 168h;Autoclave; High pressure; Compound 2 wassynthesized by loading TCPP (0.1 mmol, 79.0 mg) and 15 mL methanol into a25 mL Teflon-lined stainless steel autoclave and heating the autoclave at 443 Kfor 7 days. After cooling slowly the mixture to room temperature at 6 K/h, redcrystals suitable for X-ray analysis were collected.
  • 2
  • [ 22112-83-0 ]
  • [ 14609-54-2 ]
YieldReaction ConditionsOperation in experiment
98% With potassium hydroxide; In tetrahydrofuran; water monomer; at 75℃; for 16h; General procedure: Tetramethylester (0.593 g, 0.70 mmol) or octaethylesterporphyrin (0.834 g, 0.70 mmol) was dissolved in 100 mL THF in atwo neck round bottom flask. To this, 10 mL of aq. solution of KOH(300 equivalents) was added and refluxed for 16 h at 75 C. Aftercompletion of the reaction, THF was removed using rotary evaporatorand the resulting residue was treated with 2N HCl (150 mL)which resulted green precipitate, filtered and washed with water(50 mL x 5). The protonated porphyrin was neutralized with pyridine(15 mL). Then, the pyridine was removed by rotary evaporationand the resulting residue was washed with water (50 mL x 3)and dried under vacuum. The crude porphyrin was recrystallizedfrom CHCl3 and acetone mixture (3:7, v/v). The yield was found tobe 0.54 g (98%) for the corresponding tetraacid and 0.680 g (100%)for octaacid.
96% With methanol; water monomer; potassium hydroxide; In tetrahydrofuran; for 24h;Reflux; The prepared TCPPCOOMe (4.2 g) was stirred in a mixed solvent of tetrahydrofuran (80 mL) and methyl alcohol (80 mL),It was added to 80 ml of a KOH aqueous solution (0.24 mol, 13.5 g). after, The mixture was refluxed for 24 hours, then cooled to room temperature.Before evaporating trahydrofuran and methyl alcohol,The mixture was filtered with filter paper (grade 2, 8 μm).Additional water was added to the resulting water phase. The aqueous solution was filtered again with filter paper. after,The solution was acidified to pH 2 with 1M HCl. The precipitate is washed with water,Collected by centrifugation,TCPP was prepared by vacuum drying (Schlenk line) (4.7 mmol, 3.7 g, yield 96%).
89% With potassium hydroxide; In tetrahydrofuran; for 24h;Reflux; TCMPP(0.4g, 0.47mmol), KOH solution(20ml, 5% mass ratio) and THF(70ml) wereadded to a 150ml round-bottom flask and refluxed for 24h. The reaction wasmonitored by thin-layer chromatography (TLC). THF was removed through rotaryevaporator after the reaction was finished, and the mixture was carefully neutralizedwith dilute HCl solution to pH = 2-3. Washed the solid with distilled water for severaltimes and obtained TCPP (0.33g, yield 89%).MS (ESI): m/z = 791.5 [M+H]+, calcd. for C48H30N4O8 : 790.7; 1H NMR ( 400 MHz,DMSO, TMS) δ (ppm) = 8.82 (s, 8H, pyrrole ring), 8.25-8.38(d, 16H, -C6H4), -2.90 (s,2H, pyrrloe NH); IR (KBr) υ (cm-1) = 3635, 3315, 1710, 1605, 1475, 1401, 963
88% With water monomer; potassium hydroxide; In tetrahydrofuran; methanol; at 100℃; for 12h; The obtained <strong>[22112-83-0]TPPCOOMe</strong> (0.25 g, 2.9mmol) was added in mixed solvent of MeOH (10 mL) andtetrahydrofuran (THF, 10 mL). Then, a solution of KOH (0.49 g, 8.7 mmol, 10 mL)was introduced. After refluxing and stirring for 12 h at 100 C, THF and MeOH in theresulting solution were evaporated. Then, additional water was added to the resultingaqueous phase. The mixture was heated until solids were completely dissolved. Thehomogeneous solution was acidified with 1 mol/L HCl until no further precipitatedetected. The green solid (0.26g, 88%) was collected by filtration, washed with waterand dried in vacuum.1H NMR (400 MHz, DMSO-d6): δ 8.82 (s, 8H), 8.33 (q, J = 8.3Hz, 16H) (Fig. S3). m/z = 790.6 (Fig. S4).
80% With hydrogenchloride; In trifluoroacetic acid; at 85℃; for 36h; H2(<strong>[22112-83-0]TMCPP</strong>) (0.12 mmol) was dissolved in 5 ml of trifluoroacetic acid, then 2.5 mL of HCl (35%)was added to the solution, and the mixture was stirred at 85 C for 36 h. The reaction mixturewas diluted with cold water to give green precipitate, filtered, and washed with water andCH2Cl2 at three times to remove unreacted H2(<strong>[22112-83-0]TMCPP</strong>). The green solid was dissolved in 10 mLpyridine, filtered, and evaporated. After washing with water and CH2Cl2 to afford H2(TCPP) in80% yield as purple powder.H2(TCPP), UV-Vis (DMF) λmax, 422 (a Soret band), 515, 552,592 and 648 (Q bands).1H NMR (500 MHz, CDCl3): δ 13.3 (br, 4H), 8.84 (s, 8H), 8.37 (d, J=8.15 Hz, 8H), 8.33 (d, J=8.15 Hz,8H); 13C NMR (126 MHz, CDCl3) δ 119.78 (Cmeso), 128.35 (ArCmeta), 131.00 (C), 134.89(ArCortho), 145.84 (Cα), 167.90 (C=O). Elemental analysis: calculated for C48H30N4O8: C 72.90, H3.82, N 7.09. Found: C 72.11, H 3.67, N 6.75. High-resolution MS, calcd for C48H30N4O8: 790.2064.Found m/z: 790.0068.
60% With potassium hydroxide; In tetrahydrofuran; methanol; water monomer; for 12h;Reflux; The obtained methyl ester (0.75g, 0.885mmol) was stirred in THF/MeOH mixed solvent (50mL, 1:1 v/v), and then a solution of aqueous KOH (2.63g, 46.95mmol in H2O 25mL) was added. The resultant mixture was stirred and refluxed for 12h. After cooling down the solution to room temperature, THF and MeOH removed under reduced pressure. Further water was added to the resulting mixture in order to dissolve the solid by heating. Afterwards, the homogeneous solution was acidified by dropwise addition of 1M HCl until no further precipitate was observed. The crystals were then collected using filtration, washed with water and left to dry in air (or in vacuum) (470mg, 0.594mmol, 60 % yield).
With water monomer; potassium hydroxide; In tetrahydrofuran; at 85℃; for 12h; Mix 2 g of the synthesized porphyrin ester, 60 mL of THF, 60 mL of methanol, and a prepared potassium hydroxide (KOH) solution (6.8 g KOH plus 60 mL of water), and condense and reflux the mixture at 85 C for 12 h. After cooling to room temperature, adjust the pH of the product to 6~7 with 1M (mol/L) HCl solution, then wash with a large amount of water by suction, and finally vacuum dry at 90C for 12h to obtain tetrakis(4-carboxyphenyl) Porphyrin (H2TCPP).
With potassium hydroxide; In tetrahydrofuran; methanol; water monomer; at 80℃; for 12h; Pyrrole (3.0g, 0.043mol) and methyl p-formylbenzoate (6.9g, 0.042mol) were put into a 250ml Pyrrole (3.0g, 0.043mol), methyl p-formylbenzoate (6.9g, 0.042mol) and propionic acid (100mL) were added into a three-neck flask (250mL). The reaction was conducted at 150C for 12h. After reaction, the reaction mixture was cooled to room temperature, yielding black solid. After filtration, the solid was washed with ethanol and dried in vacuum to obtain purple porphyrin ester precursor. The precursor (1.95g) was dissolved in a mixed solvent (120mL, tetrahydrofuran / methanol=1:1). 60ml 2M KOH aqueous solution was added into the mixed solvent. The mixture was heated at 80Cfor 12h. After cooling to room temperature, the mixture was acidified with 1M HCl solution until no solid was produced. Meso-tetra(4-carboxyphenyl) porphyrin was obtained through washing operation and drying treatment. Meso-tetra(4-carboxyphenyl) porphyrin (violet crystal, 32.3%). 1H NMR (DMSO-d6): δ 2.87 ppm (2H, N-H), δ 8.39 ppm (8H, phenyl), δ 8.45 ppm (8H, phenyl), δ 8.91 ppm (8H, pyrrole).

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  • 3
  • [ 14609-54-2 ]
  • [ 22112-83-0 ]
  • 4-(10,15,20-tris(4-(methoxycarbonyl)phenyl)porphyrin-5-yl)benzoic acid [ No CAS ]
  • 4
  • [ 17114-97-5 ]
  • [ 14609-54-2 ]
  • C80H90N8O16 [ No CAS ]
  • 5
  • [ 30065-27-1 ]
  • [ 14609-54-2 ]
  • C84H62N20O8S4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% With N-ethyl-N,N-diisopropylamine; dicyclohexyl-carbodiimide; In tetrahydrofuran; at 20℃; for 48.0h; General procedure: A 25 mL round bottom flask was equipped with TCPP(100 mg, 0.126 mmol), DCC (120 mg, 0.57 mmol) andDIPEA (80 mg, 62 mmol) dissolved in THF. The whole mixturewas stirred on magnetic stirrer at room temperaturefollowed by addition of corresponding amine or hydrazide.TLC technique was used to monitor the progress of reaction.The stirring of reaction mixture was allowed until thecompletion of reaction i.e. up to 48 h. After that, the reactionmixture was extracted in ethyl acetate followed bytreatment of saturated NaHCO3 and diluted HCl solutionto expel out unreacted quantity of TCPP and amine or hydrazide,respectively. The ethyl acetate layer was dried overFig. 1 Representative structure of TCPP anhydrous Na2SO4 and evaporated to yield dark brown coloredcorresponding new porphyrin derivatives shown inFig. 2a-f. The synthetic route for proposed new porphyrinderivatives illustrates in Scheme 1. The spectral purity andformation of compounds were confirmed by analytical techniquesviz. IR, 1H NMR and mass analysis
 

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