67595-98-6Relevant articles and documents
Synthesis method of tetra (4-aminophenyl) porphyrin metal complex
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Paragraph 0049-0050; 0053, (2021/06/13)
The invention discloses a synthesis method of a tetra (4-aminophenyl) porphyrin metal complex. The method comprises the following steps: 1) taking organic acid as a solvent and pyrrole and 4-halogen benzaldehyde as substrates, and carrying out condensation reaction to obtain a (4-halogen phenyl) porphyrin solid; 2) dissolving the (4-halogen phenyl) porphyrin solid in an organic solvent, adding a metal salt, and reacting to obtain a (4-halogen phenyl) porphyrin metal complex; and 3) taking the (4-halophenyl) porphyrin metal complex and ammonia water as substrates, and carrying out carbon-nitrogen coupling reaction in the presence of a catalyst and an organic solvent to obtain the tetra (4-aminophenyl) porphyrin metal complex. The method is mild in reaction condition, low in toxicity, green and environment-friendly.
Supramolecular Catalysis of Acyl Transfer within Zinc Porphyrin-Based Metal-Organic Cages
Li, Lili,Yang, Linlin,Li, Xuezhao,Wang, Jing,Liu, Xin,He, Cheng
supporting information, p. 8802 - 8810 (2021/06/28)
To illustrate the supramolecular catalysis process in molecular containers, two porphyrinatozinc(II)-faced cubic cages with different sizes were synthesized and used to catalyze acyl-transfer reactions between N-acetylimidazole (NAI) and various pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC). A systemic investigation of the supramolecular catalysis occurring within these two hosts was performed, in combination with a host-guest binding study and density functional theory calculations. Compared to the reaction in a bulk solvent, the results that the reaction of 2-PC was found to be highly efficient with high rate enhancements (kcat/kuncat = 283 for Zn-1 and 442 for Zn-2), as well as the different efficiencies of the reactions with various ortho-substituted 2-PC substrates and NAI derivates should be attributed to the cages having preconcentrated and preoriented substrates. The same cage displayed different catalytic activities toward different PC regioisomers, which should be mainly attributed to different binding affinities between the respective reactant and product with the cages. Furthermore, control experiments were carried out to learn the effect of varying reactant concentrations and product inhibition. The results all suggested that, besides the confinement effect caused by the inner microenvironment, substrate transfer, including the encapsulation of the reactant and the release of products, should be considered to be a quite important factor in supramolecular catalysis within a molecular container.
Photocatalytic Molecular Oxygen Activation by Regulating Excitonic Effects in Covalent Organic Frameworks
Qian, Yunyang,Li, Dandan,Han, Yulan,Jiang, Hai-Long
, p. 20763 - 20771 (2020/12/23)
Excitonic effects caused by Coulomb interactions between electrons and holes play subtle and significant roles on photocatalysis, yet have been long ignored. Herein, porphyrinic covalent organic frameworks (COFs, specifically DhaTph-M), in the absence or presence of different metals in porphyrin centers, have been shown as ideal models to regulate excitonic effects. Remarkably, the incorporation of Zn2+ in the COF facilitates the conversion of singlet to triplet excitons, whereas the Ni2+ introduction promotes the dissociation of excitons to hot carriers under photoexcitation. Accordingly, the discriminative excitonic behavior of DhaTph-Zn and DhaTph-Ni enables the activation of O2 to 1O2 and O2?-, respectively, under visible light irradiation, resulting in distinctly different activity and selectivity in photocatalytic terpinene oxidation. Benefiting from these results, DhaTph-Ni exhibits excellent photocatalytic activity in O2?-engaged hydroxylation of boronic acid, while DhaTph-Zn possesses superior performance in 1O2-mediated selective oxidation of organic sulfides. This work provides in-depth insights into molecular oxygen activation and opens an avenue to the regulation of excitonic effects based on COFs.
Enthalpy—entropy compensation upon metal ion coordination with porphyrins: generalization for the free bases and doubly deprotonated macrocycles
Ivanova, Yu. B.,Koifman, O. I.,Kruk, M. M.,Pukhovskaya, S. G.
, p. 1072 - 1075 (2020/07/25)
Enthalpy—entropy compensation upon the coordination of zinc ions by porphyrins with various structural organizations of peripheral substitution in solutions at 298 K was studied. The same compensation temperature Tc was found for both free base
Efficient dye-sensitized solar cell based on a new porphyrin complex as an inorganic photosensitizer
Nasirian, Azam,Mirkhani, Valiollah,Moghadam, Majid,Tangestaninejad, Shahram,Mohammadpour Baltork, Iraj
, (2020/06/22)
Abstract: The synthesis of new porphyrin complexes that can absorb light in a broad range of the spectrum is very important for getting a high efficiency in dye-sensitized solar cells. The primary reason for using these complexes is good photophysical characteristic like good absorption and high quantum efficiency. Most of the metal porphyrin shows good photophysical characteristics with changing their ligands. In this work, the synthesis of a new Zn-porphyrin complex, that has a good spectral and electrochemical characteristic, is reported. Then, this complex is used as a dye in dye-sensitized solar cells, using titanium dioxide as a semiconductor. The application of this complex in a dye-sensitized nanocrystalline TiO2 solar cell has indicated a short circuit density of 11.60 mA, an open circuit potential of 0.65 V with an overall efficiency of 5.33%. The overall conversion efficiency of this system is due to the efficient electron injection into the conduction band during light absorption. Graphic abstract: In this work, the synthesis of a new Zn-porphyrin complex, together with its spectral and electrochemical properties, is described. The application of this complex in a dye-sensitized nanocrystalline TiO2 solar cell indicated a short circuit density of 11.60 mA, an open circuit potential of 0.65V with an overall efficiency of 5.33%.[Figure not available: see fulltext.]
Intrinsic Activity of Metal Centers in Metal-Nitrogen-Carbon Single-Atom Catalysts for Hydrogen Peroxide Synthesis
Liu, Chang,Li, Hao,Liu, Fei,Chen, Junsheng,Yu, Zixun,Yuan, Ziwen,Wang, Chaojun,Zheng, Huiling,Henkelman, Graeme,Wei, Li,Chen, Yuan
, p. 21861 - 21871 (2021/01/11)
Metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) show high catalytic activity for many important chemical reactions. However, an understanding of their intrinsic catalytic activity remains ambiguous because of the lack of well-defined atomic str
Rational Design of Crystalline Covalent Organic Frameworks for Efficient CO2 Photoreduction with H2O
Lu, Meng,Liu, Jiang,Li, Qiang,Zhang, Mi,Liu, Ming,Wang, Jin-Lan,Yuan, Da-Qiang,Lan, Ya-Qian
supporting information, p. 12392 - 12397 (2019/08/16)
Solar energy-driven conversion of CO2 into fuels with H2O as a sacrificial agent is a challenging research field in photosynthesis. Herein, a series of crystalline porphyrin-tetrathiafulvalene covalent organic frameworks (COFs) are synthesized and used as photocatalysts for reducing CO2 with H2O, in the absence of additional photosensitizer, sacrificial agents, and noble metal co-catalysts. The effective photogenerated electrons transfer from tetrathiafulvalene to porphyrin by covalent bonding, resulting in the separated electrons and holes, respectively, for CO2 reduction and H2O oxidation. By adjusting the band structures of TTCOFs, TTCOF-Zn achieved the highest photocatalytic CO production of 12.33 μmol with circa 100 % selectivity, along with H2O oxidation to O2. Furthermore, DFT calculations combined with a crystal structure model confirmed the structure–function relationship. Our work provides a new sight for designing more efficient artificial crystalline photocatalysts.
A porphyrin porous organic polymer with bicatalytic sites for highly efficient one-pot tandem catalysis
Dai, Siyuan,Gu, Zhi-Guo,Li, Tao,Li, Yunxing,Liu, Yong,Shen, Rui,Yan, Xiaodong,Zhu, Wei
, p. 822 - 825 (2019/01/21)
A novel porphyrin-based porous organic polymer PPOP-1(Pd) with bifunctional catalytic sites was constructed via imine condensation of tetra(4-aminophenyl)porphyrin and acenaphthenequinone. PPOP-1(Pd) containing Pd(ii)-porphyrin and Pd(ii)-α-diimine moieties exhibits excellent catalytic activity and outstanding reusability for tandem catalytic reactions of C-H arylation and Suzuki coupling.
Post-modified porphyrin imine gels with improved chemical stability and efficient heterogeneous activity in CO2 transformation
Liao, Peisen,Cai, Guangmei,Shi, Jianying,Zhang, Jianyong
supporting information, p. 10017 - 10024 (2019/07/04)
Efficient heterogeneous gel catalysts have been developed based on dynamic covalent chemistry and post-modification methods for the chemical fixation of CO2. Various porphyrin-based imine gels are synthesized and subsequent reduction of imine bonds and metallation with various metal centers yields gel catalysts. The gels are characterized by a number of techniques including SEM, TEM, EDX, FT-IR, CP/MAS 13C NMR, and XPS. The resulting gels not only have network structures including micro-, meso- and macropores, but also show improved chemical stability and strong interactions between CO2 and pore channels. The gel catalysts show good catalytic activity towards the cycloaddition of epoxides with CO2 to cyclic carbonates using wet gels. Post-modified gel catalysts with a Zn(ii) center (ZnTAPP-Go-r) show a high product yield and high stability with recyclability over 5 cycles.
Covalent functionalization and solubilization of multi-walled carbon nanotubes by using zinc and copper complexes of meso-tetra(4-aminophenyl) porphyrin
Prabhavathi,Yamuna,Jafer, Alifia C.
, p. 219 - 229 (2018/03/13)
Zinc (II) and copper (II) complexes of mesotetra(4-aminophenyl)porphyrin (Zn-TAP and Cu-TAP) were covalently connected to multi-walled carbon nanotube (MWCNT) through an amide linkage and characterized by using many spectroscopic techniques. Significant m
