- A Reversible Crystallinity-Preserving Phase Transition in Metal-Organic Frameworks: Discovery, Mechanistic Studies, and Potential Applications
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A quenching-triggered reversible single-crystal-to-single-crystal (SC-SC) phase transition was discovered in a metal-organic framework (MOF) PCN-526. During the phase transition, the one-dimensional channel of PCN-526 distorts from square to rectangular in shape while maintaining single crystallinity. Although SC-SC transformations have been frequently observed in MOFs, most reports have focused on describing the resulting structural alterations without shedding light on the mechanism for the transformation. Interestingly, modifying the occupancy or species of metal ions in the extra-framework sites, which provides mechanistic insight into the causes for the transformation, can forbid this phase transition. Moreover, as a host scaffold, PCN-526 presents a platform for modulation of the photoluminescence properties by encapsulation of luminescent guest molecules. Through judicious choice of these guest molecules, responsive luminescence caused by SC-SC transformations can be detected, introducing a new strategy for the design of novel luminescent MOF materials. (Figure Presented).
- Liu, Dahuan,Liu, Tian-Fu,Chen, Ying-Pin,Zou, Lanfang,Feng, Dawei,Wang, Kecheng,Zhang, Qiang,Yuan, Shuai,Zhong, Chongli,Zhou, Hong-Cai
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- Synthesis and spectroscopy of a series of substituted N-confused tetraphenylporphyrins
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A series of N-confused tetraphenylporphyrins (H2NCTPPs) with substituents on either the paraor the 3,5-positions of the meso phenyl rings were prepared using Lindsey conditions. Both electron-withdrawing and electron-donating groups were chosen in order to probe the effects of peripheral substitution on the properties of the macrocycles. The series includes 5,10,15,20-tetra-(4-R-phenyl) N-confused porphyrins (where R = bromo (1), iodo (2), cyano (3), methoxy (4), 2′,5′-dimethoxyphenyl (5), or ethynyl (6)) and 5,10,15,20-(3,5-di-ieri-butylphenyl) N-confused porphyrin (7). Absorption and steady-state fluorescence measurements were carried out, and quantum yields were measured for all compounds in both dichloromethane (CH 2Cl2) and dimethylacetamide (DMAc).
- Shaw, Janet L.,Garrison, Shana A.,Aleman, Elvin A.,Ziegler, Christopher J.,Modarelli, David A.
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- Synthesis, structure, and photophysical properties of some gadolinium(III) porphyrinate complexes
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A series of gadolinium(III) porphyrinate complexes was synthesized in moderate yield from the interaction of meso-substituted porphyrin free bases with Ln[N(SiMe3)2]3·x[LiCl(THF) 3], followed by the addition of a tripodal anion LOMe - - an effective encapsulating agent for lanthanide ions. These new complexes were fully characterized by X-ray crystallography, elemental analysis, mass spectrometry, and infrared spectroscopy. The electronic spectra show a near-infrared phosphorescence from the triplet state of the porphyrin rings and exhibit a very characteristic vibronic-structured emission. A series of gadolinium(III) porphyrinate complexes was synthesized and fully characterized by spectroscopic and X-ray crystallographic methods. The electronic spectra show near-infrared phosphorescence from the triplet state of the porphyrin rings and exhibit a very characteristic vibronic-structured emission. Copyright
- Zhu, Xun-Jin,Zhang, Tao,Zhao, Shunsheng,Wong, Wai-Kwok,Wong, Wai-Yeung
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- Cobalt single-atoms anchored on porphyrinic triazine-based frameworks as bifunctional electrocatalysts for oxygen reduction and hydrogen evolution reactions
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Designing and fabrication of highly active single-atom catalysts (SACs) with maximized atomic efficiency is highly desirable but still remains a great challenge. Herein, highly active and stable cobalt single-atoms with a Co-N4 moiety were uniformly anchored on a porous porphyrinic triazine-based framework (CoSAs/PTF) by a simple ionothermal method. Due to the abundant single-atom Co-N4 species, the hierarchical porous structure and the good conductivity, the resultant catalyst is highly active for the electrocatalytic oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). For the ORR, a more positive half-wave potential of 0.808 V (vs. RHE) was achieved, compared with commercial benchmark Pt/C (0.806 V). Furthermore, a small onset potential of 21 mV and a low Tafel slope of 50 mV per decade were obtained for the HER. The porphyrin-like structure was found to stabilize the CoSAs effectively, thus leading to long-term durability and a remarkable methanol-tolerant behavior. This bifunctional single-atom catalyst might be a promising candidate to replace Pt-based electrocatalysts in electrolysers and fuel cells.
- Yi, Jun-Dong,Xu, Rui,Chai, Guo-Liang,Zhang, Teng,Zang, Ketao,Nan, Bing,Lin, Hua,Liang, Yu-Lin,Lv, Jiangquan,Luo, Jun,Si, Rui,Huang, Yuan-Biao,Cao, Rong
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- A stable metal cluster-metalloporphyrin MOF with high capacity for cationic dye removal
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A metalloporphyrin Cu5-cluster based MOF (metal-organic framework), [Cu4.5((H4TZPP)(TZPP)Cl2)(H2O)0.5]·CH3NH2CH3·7EtOH·8H2O (LIFM-WZ-3) was synthesized from the tetrapodal ligand 5,10,15,20-tetrakis[4-(2,3,4,5-tetrazolyl)phenyl]porphyrin (H6TZPP) and copper chloride. LIFM-WZ-3 exhibits a rare 2D + 3D → 3D interpenetration topology, of which the frl-type 3D MOF and a layered 2D HOF (hydrogen bond organic framework) are intertwined, leading to an anionic framework with 1D spindle-like channels. Powder X-ray diffraction analysis reveals that the framework is stable in acid, base and various organic solvent environments. LIFM-WZ-3 exhibits moderately high separation performances for CO2/CH4, CO2/N2, C3H6/CH4, C2H6/CH4, and C2H4/CH4 at room temperature. Specifically, the anionic framework in LIFM-WZ-3 containing dimethylamine cations can selectively adsorb cationic organic dyes from aqueous pollutants for recycle purpose. The high adsorption capacity for methylene-blue (MB+, 983 mg g-1) and crystal violet (CV+, 713.5 mg g-1) ranks the highest among those MOFs ever reported.
- Wang, Zheng,Zhang, Jian-Hua,Jiang, Ji-Jun,Wang, Hai-Ping,Wei, Zhang-Wen,Zhu, Xunjin,Pan, Mei,Su, Cheng-Yong
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- Highly Selective Tandem Electroreduction of CO2 to Ethylene over Atomically Isolated Nickel–Nitrogen Site/Copper Nanoparticle Catalysts
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Herein, an effective tandem catalysis strategy is developed to improve the selectivity of the CO2RR towards C2H4 by multiple distinct catalytic sites in local vicinity. An earth-abundant elements-based tandem electrocatalyst PTF(Ni)/Cu is constructed by uniformly dispersing Cu nanoparticles (NPs) on the porphyrinic triazine framework anchored with atomically isolated nickel–nitrogen sites (PTF(Ni)) for the enhanced CO2RR to produce C2H4. The Faradaic efficiency of C2H4 reaches 57.3 % at ?1.1 V versus the reversible hydrogen electrode (RHE), which is about 6 times higher than the non-tandem catalyst PTF/Cu, which produces CH4 as the major carbon product. The operando infrared spectroscopy and theoretic density functional theory (DFT) calculations reveal that the local high concentration of CO generated by PTF(Ni) sites can facilitate the C?C coupling to form C2H4 on the nearby Cu NP sites. The work offers an effective avenue to design electrocatalysts for the highly selective CO2RR to produce multicarbon products via a tandem route.
- Cao, Rong,Hou, Ying,Huang, Yuan-Biao,Mao, Min-Jie,Meng, Dong-Li,Si, Duan-Hui,Zhang, Meng-Di
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- An ultrafast responsive NO2 gas sensor based on a hydrogen-bonded organic framework material
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We report the development of a new type of organic semiconductor gas sensor based on a porphyrin-based hydrogen-bonded organic framework (HOF). Owing to the orderly porous structures, the decoration with rich amino sites and the n-type semiconductor nature, this HOF-based sensor exhibits selective NO2 sensing performance with ultra-fast response/recovery rates (17.6 s/15.4 s over 100 ppb) and a limit of detection lower than 40 ppb, together with high sensitivity, good reproducibility, and long-term stability at room temperature. This study demonstrates that HOF-based materials have potential application prospects in gas sensing, thereby offering a new way of thinking for the design and development of sensors.
- Wang, Yijie,Liu, Di,Yin, Jianbo,Shang, Yanxue,Du, Juan,Kang, Zixi,Wang, Rongming,Chen, Yanli,Sun, Daofeng,Jiang, Jianzhuang
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- Integration of metalloporphyrin into cationic covalent triazine frameworks for the synergistically enhanced chemical fixation of CO2
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The design and preparation of porous catalysts with multiple catalytically active sites for synergistically catalytic conversion of CO2 still remains a challenge. Herein, cobalt porphyrin as a Lewis acidic active site was introduced in imidazolium-functionalized cationic covalent triazine frameworks (denoted as Co-PCCTFs) via copolymerization of cobalt 5,10,15,20-Tetrakis(4-cyanophenyl)porphyrin (Co-TPPCN) and 1,3-bis(4-cyanophenyl) imidazolium chloride ([BCIM]Cl). The obtained bifunctional Co-PCCTFs with positively charged imidazolium groups have high BET surface areas and show sufficient CO2 adsorption uptakes. The nucleophilic halide anions of the imidazolium parts and the cobalt porphyrin Lewis acid sites were positioned in close proximity so that the Co-PCCTFs could synergistically activate substrates and intermediates. Compared with ICTF-400 free of Co2+ that was obtained from [BCIM]Cl, Co-PCCTF5 exhibited enhanced activity for the cycloaddition of CO2 to epoxides to produce cyclic carbonates without a cocatalyst under mild conditions. Moreover, Co-PCCTF5 is sufficiently stable so that it could be reused more than 5 times without loss of catalytic activity. This work provides a new approach for the design and preparation of efficient multifunctional catalysts with multiple sites for synergistic catalysis.
- Cao, Rong,Chen, Jian-Xin,Huang, Yuan-Biao,Mao, Min-Jie,Wu, Qiu-Jin
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p. 8026 - 8033
(2020/12/28)
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- Selective Solvent-Free and Additive-Free Oxidation of Primary Benzylic C–H Bonds with O2 Catalyzed by the Combination of Metalloporphyrin with N-Hydroxyphthalimide
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Abstract: A protocol for solvent-free and additive-free oxidation of primary benzylic C–H bonds with O2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts to overcome the deficiencies encountered in current oxidation systems. The effects of reaction temperature, porphyrin structure, central metal, catalyst loading and O2 pressure were investigated systematically. For the optimized combination of T(2-OCH3)PPCo and NHPI, all the primary benzylic C–H bonds could be functionalized efficiently and selectively at 120 °C and 1.0?MPa O2 with aromatic acids as the primary products. The selectivity towards aromatic acids could reach up to 70–95% in the conversion of more than 30% for most of the substrates possessing primary benzylic C–H bonds in the metalloporphyrin loading of 0.012% (mol/mol). And the superior performance of T(2-OCH3)PPCo among the metalloporphyrins investigated was mainly attributed to its high efficiency in charge transfer and fewer positive charges around central metal Co (II) which favored the adduction of O2 to cobalt (II) forming the high-valence metal-oxo complex followed by the production of phthalimide N-oxyl radical (PINO) and the initiation of the catalytic oxidation cycle. This work would provide not only an efficient protocol in utilization of hydrocarbons containing primary benzylic C–H bonds, but also a significant reference in the construction of more efficient C–H bonds oxidation systems. Graphic Abstract: The solvent-free and additive-free oxidation of primary benzylic C–H bonds with O2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts, and the highest selectivity towards aromatic acid reached up to 95.1% with the conversion of 88.5% in the optimized combination of T(2-OCH3)PPCo and NHPI.[Figure not available: see fulltext.].
- Shen, Hai-Min,Qi, Bei,Hu, Meng-Yun,Liu, Lei,Ye, Hong-Liang,She, Yuan-Bin
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p. 3096 - 3111
(2020/04/29)
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- Atomic Ni Anchored Covalent Triazine Framework as High Efficient Electrocatalyst for Carbon Dioxide Conversion
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Electrochemically driven carbon dioxide (CO2) conversion is an emerging research field due to the global warming and energy crisis. Carbon monoxide (CO) is one key product during electroreduction of CO2; however, this reduction proce
- Lu, Chenbao,Yang, Jian,Wei, Shice,Bi, Shuai,Xia, Ying,Chen, Mingxi,Hou, Yang,Qiu, Ming,Yuan, Chris,Su, Yuezeng,Zhang, Fan,Liang, Haiwei,Zhuang, Xiaodong
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- Visible light photo-sensitized metallo-porphyrin/TiO2 photocatalyst and its related self-cleaning effects in poly ethylene terephthalate
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Dye degrading property to exhibit self-cleaning effect in Poly Ethylene Terephthalate (PET) through photocatalytic effect by Metallo porphyrin and TiO2 has been studied in detail. PET has been modi?ed by step wise deposition of anatase TiO2 and Metallo po
- Heo, Gisu,Manivannan, Ramalingam,Kim, Hyorim,Won Ryu, Ji,Son, Young-A
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p. 8004 - 8012
(2019/07/16)
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- Zinc porphyrin complex used for electrocatalysis oxygen evolution reaction, and preparation method thereof
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The invention discloses a zinc porphyrin complex used for electrocatalysis oxygen evolution reaction, and a preparation method thereof. The molecular formula of the zinc porphyrin complex is Zn(CNTCPP), wherein Zn is a divalent ion, CNTCPP is 5,10, 15, 20-tetracyanide phenyl porphyrin ligand; the structure of the zinc porphyrin complex belongs to monoclinic system P2/n space group; the crystal basic structure unit is obtained from an asymmetric unit via symmetry operation; symmetry operation codes are x, y, z; 0.5-x, 0.5+y, 0.5-z; -x, -y, -z; 0.5+x, 0.5-y, 0.5+z; the asymmetric unit is composed of a ligand CNTCPP and Zn, lattice parameters axial length a=9.7858(3) angstroms, b=9.3797(2) angstroms, c=21.3172(5) angstroms; axial angle alpha=90.00 DEG, beta=100.777(3) DEG, gamma=90.00 DEG; unit cell size V=1922.15(9) angstroms3, Z=2. The advantages are that: 1, the reaction solvent is easily available, cheap, and green, and no pollution is caused; 2, reaction conditions are simple, reaction can be realized quickly, energy is saved, and time is saved; and 3, yield is high, ligand using amount is low, and cost is low.
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Paragraph 0034; 0035; 0036
(2017/10/07)
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- Study on a series of novel self-assembly supramolecular solar cells based on a double-layer structured chromophore of Zn-porphyrins
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We prepared in this work an anchoring porphyrin and a series of hat-porphyrins. The zinc atom of the hat-porphyrins can be coordinated axially with the pyridine moiety of the anchoring porphyrin which is anchored on the titania surface by a carboxyl group. The structures of the assemblies were confirmed using computational calculations, transmission electron microscopy (TEM) and energy dispersive spectrometry (EDS). Solar cell devices of the monomer anchoring porphyrin and its assemblies were fabricated and the photovoltaic performances were measured under standard AM 1.5 sunlight irradiance. We found that the assembly devices showed higher JSC and lower VOC than that of the monomer anchoring porphyrin device. However, the comprehensive influence of JSC and VOC led to an enhancement in the solar-to-electric power-conversion efficiency (PCE) of the assemblies. We also studied the variation of JSC and VOC using electronic absorption and emission spectroscopy, charge extraction measurements, transient photovoltage decay measurements and electrochemical impedance spectroscopy.
- Han, Fa-Ming,Yang, Jiong-Yuan,Zhe, Ying,Chen, Ji-Wen,Liu, Jia-Cheng,Li, Ren-Zhi,Jin, Xiao-Jie,Zhao, Guo-Hui
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supporting information
p. 8862 - 8868
(2016/06/09)
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- Synthesis, circular dichroism, DNA cleavage and singlet oxygen photogeneration of 4-amidinophenyl porphyrins
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5,10,15,20-tetrakis(4-amidinophenyl)porphyrin (Por 1), its Zn complex (Por 2) and its conjugate with a tetraphenylporphyrin to form a bisporphyrin (Por 3) were prepared. The monomeric Por 1 and Por 2 showed both intercalative and external binding with DNA whereas only external DNA binding was seen in the bisporphyrin, Por 3 by circular dichroism and UV-vis. The DNA photocleavage activities of these porphyrins followed the order: Por 1 ~ Por 2 > Por 3, which did not correlate with their measured 1O2 production rates. It suggests 4-amidinophenylporphyrins are promising new photodynamic therapeutic agents.
- Wang, Kai,Poon, Chun T.,Choi, Chun Y.,Wong, Wai-Kwok,Kwong, Daniel W.J.,Yu, Fa Q.,Zhang, Heng,Li, Zao Y.
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experimental part
p. 85 - 92
(2012/07/17)
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- Synthesis of biladienone and bilatrienone by coupled oxidation of tetraarylporphyrins
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(Chemical Equation Presented) Tetraarylbiladien-ab-ones bearing various substituents (R) in the para position of the phenyl groups were preprared by coupled oxidation of tetraarylporphyrin iron complexes. The yields of 5,10,15-triaryl-19-aroyl-15-hydroxyb
- Asano, Naomi,Uemura, Sayo,Kinugawa, Tomoya,Akasaka, Hiroaki,Mizutani, Tadashi
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p. 5320 - 5326
(2008/02/07)
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- Synthesis of calix[3]dipyrrins by a modified Lindsey protocol
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(Figure Presented) Bowled over: Calix[3]dipyrrins were synthesized from pyrrole and aryl aldehyde precursors by the Lindsey protocol, modified by the presence of a small amount of water. These bowl-shaped macrocycles can accommodate three metal (M) ions such as NiII and CuII in a hexagonal M3O3 manner (see structure; Cu green, N blue, O red, C black).
- Inoue, Mitsunori,Ikeda, Chusaku,Kawata, Yuji,Venkatraman, Sundararaman,Furukawa, Ko,Osuka, Atsuhiro
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p. 2306 - 2309
(2008/03/12)
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- Aspects of investigating scrambling in the synthesis of porphyrins: Different analytical methods
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Herein, we discuss the analyses and quantification of the different components in porphyrin mixtures, prepared from p-anisaldehyde, p-tolualdehyde, and 5-(4-bromophenyl)-dipyrromethane with acid catalysis, using NMR and HPLC. The advantages and disadvantages of these analytical methods are emphasized. Due to the similar size of a bromine atom and a methyl group it was possible to grow crystals suitable for X-ray crystallographic studies from a mixture of porphyrins, where the 4-position of the meso-phenyl rings was either substituted with methyl groups or bromine atoms. We also show that X-ray studies are inferior to NMR analysis for determining the components in a porphyrin mixture.
- Nielsen, Christian B.,Krebs, Frederik C.
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p. 5935 - 5939
(2007/10/03)
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- Novel synthesis of meso-tetraarylporphyrins using CF3SO 2Cl under aerobic oxidation
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meso-Tetraarylporphyrins are synthesized from pyrrole and aryl aldehydes cleanly and efficiently in one pot at room temperature using equimolar amount of CF3SO2Cl in the presence of air as oxidant. By this novel method 5,10,15,20-tetraarylporphyrins can be prepared in excellent yields.
- Sharghi, Hashem,Nejad, Alireza Hassani
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p. 1863 - 1868
(2007/10/03)
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- Phosphorus pentachloride (PCl5) mediated synthesis of tetraarylporphyrins
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A new synthesis of porphyrins from pyrrole and substituted benzaldehydes is described, with PCl5 as catalyst. Aromatic aldehydes condense irreversibly with pyrrole in the presence of this catalyst, and aerobic oxidation of porphyrinogen provides functionalized porphyrins in yields of 20-65%.
- Sharghi, Hashem,Nejad, Alireza Hassani
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p. 408 - 414
(2007/10/03)
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- Synthesis of meso-tetraarylporphyrins in air with silica chloride as catalyst
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Meso-tetraarylporphyrins (14 examples) are prepared efficiently by condensation of pyrrole with aromatic aldehydes in the presence of silica chloride, followed by air oxidation. The method is compared with other published procedures.
- Sharghi, Hashem,Nejad, Ali Reza Hassani
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- Superoxide dismutase mimetics: synthesis and structure-activity relationship study of MnTBAP analogues.
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Carboxylic ester and amide-substituted analogues of [5,10,15,20-tetrakis(4-carboxyphenyl)-porphyrinato]manganese(III) chloride (MnTBAP) were synthesized and assayed as potential superoxide dismutase (SOD) mimetics. The tetraester analogues 4a and 4b were
- Gauuan, Polivina Jolicia F,Trova, Michael P,Gregor-Boros, Livia,Bocckino, Stephen B,Crapo, James D,Day, Brian J
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p. 3013 - 3021
(2007/10/03)
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- Rothemund and Adler-Longo Reactions Revisited: Synthesis of Tetraphenylporphyrins under Equilibrium Conditions
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We present a new synthetic strategy for preparing tetraphenylporphyrins that should greatly expand synthetic entries into porphyrin containing model systems.Pyrrole and the desired benzaldehyde react reversibly at room temperature with trace acid catalysis to form the cyclic tetraphenylporphyrinogen at thermodynamic equilibrium.An oxidant is then added to irreversibly convert the porphyrinogen to the porphyrin.The greater stability of the cyclic porphyrinogen over the open-chain polypyrrylmethanes occurs when the reaction is performed at moderate dilution (10-2 M).The reaction at high dilution or high concentration affords a negligible yield of the cyclic porphyrinogen.Porphyrinogen exchange reactions provide proof of equilibrium.This methodology is complementary to the Adler-Longo procedure, allowing small quantities of porphyrins to be prepared from sensitive aldehydes in 30-40percent yield without difficult purification problems.This methodology is also extended to the preparation of meso-tetraalkylporphyrins and one hybrid porphyrin containing both aryl and alkyl substituents.The mild reaction conditions and convenience of this method permit consideration of new design strategies in preparing complex porphyrins.
- Lindsey, Jonathan S.,Schreiman, Irwin C.,Hsu, Henry C.,Kearney, Patrick C.,Marguerettaz, Anne M.
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p. 827 - 836
(2007/10/02)
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