167482-98-6Relevant articles and documents
The highly efficient and stable Cu, Co, Zn-porphyrin–TiO2 photocatalysts with heterojunction by using fashioned one-step method
Zhao, Xin,Liu, Xiao,Yu, Mimi,Wang, Chen,Li, Jun
, p. 648 - 656 (2017)
A new series of carboxyl porphyrins with different center metals (Cu, Co, Zn) insertion has been successfully synthesized. Their corresponding CuCPp–TiO2, CoCPp–TiO2, and ZnCPp–TiO2 photocatalysts were obtained under a one-pot solvothermal condition. Characterization of these composites can be achieved by both spectroscopic techniques and nitrogen adsorption–desorption measurements. The findings indicate that the MCPp–TiO2 (M(II)?=?Cu, Co, Zn) composite photocatalysts, formed by the accumulation of disperse spherical nanoparticles, possess heterogeneous structure and large surface area, resulting in the photodegradation of 4-nitrophenol (4-NP) efficiently. The metalloporphyrins with carboxyl group display superior catalytic activities due to the strong interactions between [sbnd]COOH and TiO2. The order for the photocatalytic activities is as follows: CuCPp–TiO2?>?CoCPp–TiO2?≥?ZnCPp–TiO2?>?bare TiO2. The reason for the high photocatalytic activity in CuCPp–TiO2 photocatalyst can possibly be explained by the fact that Cu(II) is more readily gaining an electron to reach a steady state, causing the isolation of electrons with holes compare to Co(II) and Zn(II) in MCPp–TiO2 composites. This possible mechanism of photocatalytic efficiencies was proposed based on the multiple tests. The findings of MCPp–TiO2 photocatalysts tests suggested that the metalloporphyrin-based MCPp–TiO2 composite photocatalysts are capable of maintaining superior stability in photocatalysis experiments even after six times cycling.
Mechanical Fixation by Porphyrin Connection: Synthesis and Transport Studies of a Bicyclic Dimer
Zwick, Patrick,Weiland, Kevin J.,Malin?ík, Juraj,Stefani, Davide,H?ussinger, Daniel,Van Der Zant, Herre S. J.,Duli?, Diana,Mayor, Marcel
, p. 118 - 128 (2020)
The bowl-shaped, 3-fold interlinked porphyrin dimer 2 was obtained in respectable yields during macrocyclization attempts. Its bicyclic structure, consisting of a macrocycle made of a pair of acetylene interlinked tetraphenylporphyrins which are additionally linked by a C-C bond interlinking two pyrrole subunits, has been confirmed spectroscopically (2D-NMR, UV/vis, HR-MALDI-ToF MS). Late-stage functionalization provided the structural analogue 1 with acetyl-protected terminal thiol anchor groups enabling single molecule transport investigations in a mechanically controlled break junction experiment. The formation of single-molecule junctions was observed, displaying large variations in the observed conductance values pointing at a rich diversity in the molecular junctions.
A C84 selective porphyrin macrocycle with an adaptable cavity constructed through alkyne metathesis
Zhang, Chenxi,Long, Hai,Zhang, Wei
, p. 6172 - 6174 (2012)
A bisporphyrin macrocycle was constructed from a porphyrin-based diyne monomer in one step through alkyne metathesis. The fullerene binding studies (C60, C70 and C84) showed the highest binding affinity of the macrocycle for C84, which is in great contrast to its bisporphyrin four-armed cage analogue that showed the strongest binding with C70.
Molecular-strain engineering of double-walled tetrahedra
Bian, Lifang,Jiang, Liang,Liang, Yimin,Liu, Jiali,Liu, Zhichang,Lu, Xingyu,Miao, Xiaohe,Tang, Min,Wang, Shangshang,Wu, Lin
, p. 2160 - 2174 (2021)
The synthesis of multi-walled nanostructures represents a formidable challenge owing to the limitations imposed by existing synthetic strategies. Herein, we report a strategy involving molecular-strain engineering (MSE) for constructing double-walled polyhedra from strained bow-shaped macrocycles called molecular bows (MBs). As a proof of concept, four double-walled tetrahedra have been assembled from L-shaped dual-panels subtending ～70.5° and producing MBs, which incorporate porphyrin and o-xylylene units, forming strained shape-persistent conformations. The head-to-tail closed-loop stacking of these units, driven by complementary non-covalent bonding interactions, leads to a large porphyrin-lined tetrahedron encapsulating a small o-xylylene-lined tetrahedron. The synergistic aromatic shielding effects emanating from the porphyrin tetrahedron result in the largest upfield chemical shifts of ?7.7 ppm for protons and ?8.8 ppm for carbons from those for the free dual panels. This demonstration, which features the launching of MSE for constructing sophisticated supramolecular nanostructures, could herald a fresh approach to the fabrication of multi-porphyrin photocatalytic systems.
Synthesis, structure, photophysical, electrochemical properties and antibacterial activity of brominated BODIPYs
Prasannan, Dijo,Raghav, Darpan,Sujatha, Subramaniam,Hareendrakrishna Kumar, Haritha,Rathinasamy, Krishnan,Arunkumar, Chellaiah
, p. 80808 - 80824 (2016/09/09)
A series of mono- and di-brominated BODIPYs (1-5) was synthesized and characterized with a view to study the performance of dyes towards antibacterial activity. Regioselective bromination at the 2- and 2,6-positions of the BODIPY core was achieved with quantitative yield. The bromination of meso-(4-hydroxyphenyl) BODIPY (5) yielded an unexpected dibromo derivative, where the bromine groups were installed at the 3,5-positions of the phenyl ring rather than the 2,6-positions of the BODIPY core, which is confirmed and supported by UV-visible, fluorescence, and 1H NMR spectroscopic analyses, electrochemical studies, and also by single crystal X-ray crystallography. We observed a red shift of ～16 nm in the absorption and 20-29 nm in the emission spectra in CH2Cl2 for the installation of each bromine group at the BODIPY core. The small difference between the first reduction potentials of the parent and dibromo derivative (5 and 5b) reveal that dibromination does not occur on the pyrrolic moiety. The intermolecular interactions involving C?H, F?H, H?H, and Br?H are the key factors in stabilizing the molecular crystal packing. The antibacterial properties of these dyes were investigated and the brominated derivatives showed better antibacterial effects than their corresponding parent BODIPYs, particularly the unusual dibromo derivative, 5b.
ABC-type meso-triaryl-substituted subporphyrins
Yoshida, Kota,Mori, Hirotaka,Tanaka, Takayuki,Mori, Tadashi,Osuka, Atsuhiro
, p. 3997 - 4004 (2014/07/08)
ABC-Type subporphyrins 5a-5h, which bear three different meso-aryl substituents, were rationally synthesized by condensation of AB-type tripyrranes and aroyl chlorides. ABC-Type subporphyrins 5i and 5j were synthesized by Pd-catalyzed amination reaction of 4-bromophenyl subporphyrins 5e and 5h, respectively. Comparative studies on these ABC-type subporphyrins with A 3-type subporphyrins and A2B-type subporphyrins revealed that substituent effects are mostly simple superpositions of individual substituents but cooperative effects are recognized for subporphyrins which bear both electron-donating and electron-withdrawing substituents. Despite extensive attempts, enantiomeric separation of B-methoxy ABC-type subporphyrins was unsuccessful, whereas B-phenylated ABC-type subporphyrins were separated to pure enantiomers. Separated enantiomers showed weak but distinct CD signals reflecting the chiral clockwise/anticlockwise arrangements of the meso-aryl substituents. These results suggest facile racemization through S N1-type heterolysis of the B-OMe bond in solution. ABC-Type meso-triaryl-substituted subporphyrins were rationally synthesized. Cooperative substituent effects are noted for donor-acceptor-type subporphyrins. Although the chiral resolution has not been successful for B-methoxy ABC-type subporphyrins, the enantiomers of some B-phenyl subporphyrins have been resolved by using chiral HPLC. Copyright
SYNTHETIC ROUTE TO ABCD-PORPHYRINS
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Page/Page column 25; 42, (2008/12/08)
A method of making a metalloporphyrin is carried out by reacting (i) a linear tetrapyrrole, said linear tetrapyrrole having a 19-acyl group and a 1-protecting group, with (ii) a metal salt under basic conditions to produce the metalloporphyrin. Products produced by such methods and intermediates useful for carrying out such methods are also described.
Synthesis of tetraphenylsubstituted porphyrins by interaction of 5-aryldipyrromethanes with 4-substituted benzaldehydes
Rumyantseva,Khabarova,Cheshkov,Fedorova,Mironov
body text, p. 762 - 767 (2009/04/18)
Synthesis of tetraphenyl substituted porphyrins with tert-butyl and methoxycarbonyl groups in meso-aryl radicals is described. It is shown that, during the condensation of dipyrromethanes with substituted benzaldehydes, a rearrangement occurs with the formation of a mixture of isomeric porphyrins. The character of these rearrangements depends on the position of substituents in the starting compounds.
New route to ABCD-porphyrins via bilanes
Dogutan, Dilek Kiper,Zaidi, Syeda Huma H.,Thamyongkit, Patchanita,Lindsey, Jonathan S.
, p. 7701 - 7714 (2008/03/11)
(Chemical Equation Presented) A new strategy for preparing porphyrins that bear up to four different meso-substituents (ABCD-porphyrins) relies on two key reactions. One key reaction entails a directed synthesis of a 1-protected 19-acylbilane by acid-catalyzed condensation at high concentration (0.5 M) of a 1-acyldipyrromethane and a 9-protected dipyrromethane-1-carbinol (derived from a 9-protected 1-acyldipyrromethane). Three protecting groups (X) were examined, including thiocyanato, ethylthio, and bromo, of which bromo proved most effective. The bilanes were obtained in 72-80% yield, fully characterized, and examined by 15N NMR spectroscopy. The second key reaction entails a one-flask transformation of the 1-protected 19-acylbilane under basic, metal-templating conditions to give the corresponding metalloporphyrin. The reaction parameters investigated for cyclization of the bilane include solvent, metal salt, base, concentration, temperature, atmosphere, and time. The best conditions entailed the 1-bromo-19-acylbilane at 100 mM in toluene containing DBU (10 mol equiv) and MgBr2 (3 mol equiv) at 115°C exposed to air for 2 h, which afforded the magnesium porphyrin in 65% yield. The magnesium porphyrin is readily demetalated to give the free base porphyrin. A stepwise procedure (which entailed treatment of the 1-(ethylthio)-19-acylbilane to oxidation, metal complexation, desulfurization, carbonyl reduction, and acid-catalyzed condensation) was developed but was much less efficient than the one-flask process. The new route to ABCD-porphyrins retains the desirable features of the existing "2 + 2" (dipyrromethane + dipyrromethane-1,9-dicarbinol) method, such as absence of scrambling, yet has significant advantages. The advantages include the absence of acid in the porphyrin-forming step, the use of a metal template for cyclization, the ability to carry out the reaction at high concentration, the lack of a quinone oxidant, avoidance of use of dichloromethane, and the increased yield of macrocycle formation to give the target ABCD-metalloporphyrin.
Methods and intermediates for the synthesis of dipyrrin-substituted porphyrinic macrocycles
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Page/Page column 5, (2010/02/09)
The present invention provides dipyrrin substituted porphyrinic macrocycles, intermediates useful for making the same, and methods of making the same. Such compounds may be used for purposes including the making of molecular memory devices, solar cells and light harvesting arrays.
