The Porphyrin Handbook Synthesis And Organic Chemistry Volume 1 Pdf
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- The Porphyrin Handbook Multporphyrins Multiphthalocyanines And Arrays
- Synthesis and Properties of Metal Phthalocyanines Containing Azo Chromophores
- A Synthetic Approach of New Trans-Substituted Hydroxylporphyrins
Editors K. Kevin M.
Box , Heraklion , Crete, Greece. All of the synthesized products were characterized by 1 H -N. Electrochemical studies revealed two one-electron oxidations and two reductions. In addition, the X-ray structure of one methoxy-derivative was determined. In the last years porphyrin derivatives have been developed or are under development for use as photosensitizers for photoelecronic materials such as sensors [ 1 ] and photosensitized solar cells [ 2 ].
The Porphyrin Handbook Multporphyrins Multiphthalocyanines And Arrays
UV-visible absorption spectra and X-ray crystal structure analyses revealed that the presence of a methoxycarbonyl substituent did not influence the deformation of the molecular framework and its absorption properties; this is because the methoxycarbonyl has a planar and perpendicular geometry, as opposed to the relatively bulky trifluoromethyl substituent.
Porphyrins, which are naturally occurring aromatic compounds, are widely distributed in fundamental indispensable biosystems in the form of heme or chlorophyll, and they play essential biological roles. Many scientists have attempted to mimic or improve the functions of porphyrins by modifying their structures and electronic properties.
This is because such modifications would allow us to probe the origin of life and aid the design of compounds having potential applications in advanced materials science [ 1 , 2 ].
Incorporating diverse substructures into the porphyrin core is an effective way to induce deformation of the framework, and the consequent non-planarity is one of the prevalent mechanisms for the activation of natural porphyrins [ 3 , 4 ]. The introduction of perfluoroalkyl groups is expected to result in drastic perturbations in the molecule owing to their sterically bulky three-dimensional structure and strong electron-withdrawing nature.
Some chemists have demonstrated that meso -perfluoroalkyl-substituted porphyrins have superior functionalities as compared to previously reported examples [ 5 , 6 , 7 , 8 ]. Recently, we reported the unexpected formation of 5-trifluoromethyl-2,3,7,8,12,13,17,octaalkylporphyrins and revealed that a trifluoromethyl group has both steric and electronic effects as expected, so that we could access distorted frameworks that show red-shifted light absorption [ 11 ].
Herein, we report the synthesis of a meso -CF 3 substituted octaalkylporphyrin via another novel and optimized substitution reaction. We also report an inner-metal dependent solvolysis reaction, whereby the CF 3 substituents are converted into methoxy-carbonyl groups. We investigated various reaction conditions to improve the product yield. The reaction mixture was diluted with CHCl 3 , and the resulting solution was stirred for up to 8 h at room temperature, followed by the addition of DDQ.
Unfortunately, no improvement in yields of 6 , 7 , and 8 was observed. After 8 h of stirring with TFA, which was a sufficiently long reaction time like that of the previous conditions, followed by the usual oxidation and work-up procedures, a predominant product 9 was obtained. In this case, 3 , 4 , and 5 were not formed or were detected in only trace amounts Scheme 2. The colors of 4 and 5 in similar solvents were light green and deep purple, respectively; thus, 9 was deemed different from either 4 or 5 [ 11 ].
The UV-visible absorption spectrum of 9 recorded in CH 2 Cl 2 displayed a Soret-band-like band at nm and Q-band-like bands at , , , and nm, indicating that 9 was a type of porphyrin Figure 1. These results indicated that 9 possessed two CF 3 groups at the porphyrinic meso -positions but its spectra were not identical those of 5. Therefore, we assigned the structure of 9 as shown in Scheme 2. The meso -CF 3 substituted porphyrin derivatives 4 , 7 , and 9 could encapsulate several ordinary metal ions such as Zn, Cu, Ni, and Pd.
The conversion was almost quantitative in all cases except for zinc, which afforded a minor side product, when it was left for a long time as a mixture. Single crystals of zinc complexes 7Zn and 9Zn were grown from CHCl 3 solutions by vapor diffusion of methanol. Initially, we believed that we obtained crystals of 7Zn and 9Zn suitable for X-ray diffraction analyses. However, the data generated unusual electron density maps that were different from those of the expected structures.
Surprisingly, solvolytic side reactions had occurred such that the CF 3 substituents were converted into methoxycarbonyl CO 2 Me. Isolated 7Zn and 9Zn also undertook solvolyses without excess zinc salts Scheme 3 , whereas the other metal complexes Cu, Ni, Pd did not cause under the similar conditions.
As illustrated in Figure 1 , the UV-visible absorption spectrum of 9Zn exhibited a Soret band at nm, which was red-shifted compared to that of the corresponding free base 9 , while the lowest energy Q-band was at nm.
With the X-ray diffraction data of 11Zn and 12Zn in hand, we examined the structural features of these macrocycles.
We have already reported the relationship between the number of CF 3 substituents and the deviation of the macrocycle from planarity in the free-base and nickel-complex forms. This release occurs because a CO 2 Me substituent is flat and can orient perpendicular against the macrocyclic plane, whereas a CF 3 substituent is three-dimensionally bulky. Mean-plane deviations calculated from the core 24 atoms of 11Zn and 12Zn were 0. Figure 3 indicates that the 5-position in compound 7 , substituted with the CF 3 group, showed a greater deviation from the mean plane than did the other meso -positions of 7.
However, since the 5-position of 11Zn or the 5,positions of 12Zn were substituted with CO 2 Me, their skeletons deviated from the mean planes only to a small extent.
The angle made by C 5 -CO 2 Me bond against the mean plane was 9. The N-Zn distances and the displacement of the Zn atoms from the mean-plane were 2. Crystal structures of a 11Zn ; b 12Zn. Upper: top view; lower: side view. Mean plane deviation diagrams of 7 [ 5 ], 11Zn , and 12Zn.
All reagents were of the commercial reagent grade and were used without further purification. Preparative separations were performed by silica gel gravity column chromatography Wako gel CHG. A solution of 1 3. CHCl 3 57 mL was added and the resulting solution was stirred for 8 h at room temperaure, followed by addition of DDQ 2.
After 30 min, the reaction mixture was passed through a short alumina column with CHCl 3 and the solution was evaporated to dryness. The first moving olive-green fraction was collected and evaporated. The resulting solution was washed with water twice and dried over anhydrous sodium sulfate. After removal of the solvent, 7Zn was obtained almost quantitatively. After removal of the solvent, 9Zn was obtained almost quantitatively. A solution of 7Zn A solution of 9Zn The synthesis of such a cis -configured porphyrin is usually challenging because more complicated oligo-pyrrolic precursors containing CF 3 substituent may be required.
Compared with its trans -analogue 5 , the cis -configured 9 showed more red-shifted absorption bands, suggesting that a cis -arrangement worked more effectively than a trans -arrangement for extension of the absorption range Figure S In this regard, the compounds generated via our protocol can be useful scaffolds for novel functional molecular assemblies.
Further investigations for utilizing these methodologies are ongoing in our laboratory. National Center for Biotechnology Information , U. Journal List Molecules v. Published online Feb Neves, Academic Editor and M. Amparo F. Faustino, Academic Editor. Author information Article notes Copyright and License information Disclaimer.
Received Jan 9; Accepted Feb Associated Data Supplementary Materials moleculess Keywords: porphyrin, trifluoromethyl, alkoxycarbonyl, solvolysis. Introduction Porphyrins, which are naturally occurring aromatic compounds, are widely distributed in fundamental indispensable biosystems in the form of heme or chlorophyll, and they play essential biological roles. Results and Discussion We investigated various reaction conditions to improve the product yield. Open in a separate window. Figure 1.
Metallation Reaction The meso -CF 3 substituted porphyrin derivatives 4 , 7 , and 9 could encapsulate several ordinary metal ions such as Zn, Cu, Ni, and Pd.
X-ray Crystal Structures With the X-ray diffraction data of 11Zn and 12Zn in hand, we examined the structural features of these macrocycles. Figure 2. Figure 3. Experimental Section 3. General Information All reagents were of the commercial reagent grade and were used without further purification. Syntheses 5,Bis trifluoromethyl -2,3,7,8,12,13,17,octamethylporphyrin 9. Scheme 1. Scheme 2. Scheme 3. Supplementary Materials Click here for additional data file.
Conflicts of Interest The authors declare no conflict of interest. References and Notes 1. Chambron J. In: The Porphyrin Handbook. Kadish K. Ali H. In: Handbook of Porphyrin Science. Volume 4 World Scientific; Singapore: Shelnutt J. Nonplanar porphyrins and their significance in proteins.
Senge M. Exercises in molecular gymnastics-bending, stretching and twisting porphyrins. Di Magno S. Fluorous biphasic singlet oxygenation with a perfluoroalkylated photosensitizer. Lahaye D. Design and synthesis of manganese porphyrins with tailored lipophilicity: Investigation of redox properties and superoxide dismutase activity.
Jin L. Wickramasinghe A. Smith K. Synthesis and organic chemistry. In: Kadish K.
Synthesis and Properties of Metal Phthalocyanines Containing Azo Chromophores
Neo-confused porphyrins neo-CPs , porphyrin isomers with a 1,3-connected pyrrolic subunit, are aromatic structures with a CNNN coordination core. Previously, examples of neo-CPs with fused benzo units or electron-withdrawing ester substituents have been described. In this paper, two new examples of neo-CPs are reported that lack a fused aromatic unit or an ester moiety, but instead have a bromo or phenyl substituent on the neo-confused ring. These porphyrin analogues had slightly reduced diatropic ring currents and slowly decomposed in solution. The related palladium II and nickel II complexes proved to be very unstable, even though the diatropicity of the macrocycle was enhanced. This study shows that stabilizing substituents are necessary for investigations into this class of porphyrinoids. Attempts to prepare imidazole versions of neo-CPs were unsuccessful.
PDF (48 KB). Get e- Because porphyrin research expands many fields of science, the handbook is divided into the following volumes: Volume 1, Synthesis and Organic Chemistry; Volume 2, Heteroporphyrins, Expanded.
A Synthetic Approach of New Trans-Substituted Hydroxylporphyrins
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UV-visible absorption spectra and X-ray crystal structure analyses revealed that the presence of a methoxycarbonyl substituent did not influence the deformation of the molecular framework and its absorption properties; this is because the methoxycarbonyl has a planar and perpendicular geometry, as opposed to the relatively bulky trifluoromethyl substituent. Porphyrins, which are naturally occurring aromatic compounds, are widely distributed in fundamental indispensable biosystems in the form of heme or chlorophyll, and they play essential biological roles.
The Porphyrin Handbook: Applications of Phthalocyanines. Kevin M Smith books and biography Waterstones. The Porphyrin Handbook, Volume Multiporphyrins, Multiphthalocyanines and Arrays provides information pertinent to every aspect of the chemistry, synthesis, spectroscopy, and structure of phthalocyanines This book examines the biology and medical implications of porphyrin systems. Professor Alan Rowan - Confucius Institute. Professor Alan Rowan has a research focus on the interaction of cells with nanostructured materials and surfaces Professor Rowan is an experienced physical materials chemist with a track record in fundamental and applied research in novel molecules and materials for applications in field as wide as catalysis, nanoelectronics, biomimetic machines and more recently synthetic extracellular matrices. Everybody Up: 1: Workbook, Volume 1, , 80 pages, Kathleen. The Porphyrin Handbook represents a timely publication dealing with the recent chemistry, physics, biology, and medicine of porphyrins and related macrocycles This publication will be a major reference source in this field for the new millennium.
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