133671-91-7Relevant academic research and scientific papers
Selective Extraction of C70 by a Tetragonal Prismatic Porphyrin Cage
Shi, Yi,Cai, Kang,Xiao, Hai,Liu, Zhichang,Zhou, Jiawang,Shen, Dengke,Qiu, Yunyan,Guo, Qing-Hui,Stern, Charlotte,Wasielewski, Michael R.,Diederich, Fran?ois,Goddard, William A.,Fraser Stoddart
, p. 13835 - 13842 (2018)
Along with the advent of supramolecular chemistry, research on fullerene receptors based on noncovalent bonding interactions has attracted a lot of attention. Here, we present the design and synthesis of a cationic molecular cage: a cyclophane composed of two tetraphenylporphyrins, bridged face-to-face by four viologen units in a rhomboid prismatic manner. The large cavity inside the cage, as well as the favorable donor-acceptor interactions between the porphyrin panels and the fullerene guests, enables the cage to be an excellent fullerene receptor. The 1:1 host-guest complexes formed between the cage and both C60 and C70 were characterized in solution by HRMS and NMR, UV-vis and fluorescence spectroscopies, and confirmed in the solid state by single-crystal X-ray diffraction analyses. The results from solution studies reveal that the cage has a much stronger binding for C70 than for C60, resulting in a selective extraction of C70 from a C60-enriched fullerene mixture (C60/C70 = 10/1), demonstrating the potential of the cage as an attractive receptor for fullerene separation.
Synthesis and Characterization of the First Water-Soluble Closely Interspaced Cofacial Porphyrin Dimer
Karaman, Rafik,Bruice, Thomas R.
, p. 3470 - 3472 (1991)
The first closely spaced quadruply bridged water-soluble cofacial dimer (5) was succesfully synthesized by the reaction of porphyrin 2 with sulfonamide 3 followed by N-methylation with methyl iodide.The conformations of 5 and its precursor 4 are largely dependent on the solvent, and the solvent effect is inhibited by protonation or metalation of the porphyrin cores.
Symmetrical and unsymmetrical quadruply Aza bridged closely interspaced cofacial Bis(5,10,15,20-tetraphenylporphyrin)s. 2. Synthesis, characterization, and conformational effects of solvents
Karaman, Rafik,Blaskó, Andrei,Almarsson, ?rn,Arasasingham, Ramesh,Bruice, Thomas C.
, p. 4889 - 4898 (1992)
Several water- and non-water-soluble symmetrical and unsymmetrical quadruply aza bridged closely interspaced cofacial bis(5,10,15,20-tetraphenylporphyrin)s have been synthesized and fully characterized by 2D 1H-1H NMR (COSY), 2D 13C-1H NMR, FABMS, UV/vis, IR, and fluorescence spectral techniques. It was established, on the basis of 1H NMR, UV/vis, and emission spectrophotometries, that tetrakis[m,m-(methylene(m-pyridinesulfonyl)imino)methylene]-strati-bis-(5,10,15, 20-tetraphenylporphyrin) (5), tetrakis[m,m-(methylene(m-pyridiniumsulfonyl)imino)methylene]-strati-bis-(5,10, 15,20-tetraphenylporphyrin) chloride (7), and tetrakis[m,m-(methylene(p-toluenesulfonyl)imino)methylene]-strati-bis(5,10,15, 20-tetraphenylporphyrin) (11) exist in more than one conformation in DMSO and in only one symmetrical conformation in CHCl3. The biszinc and tetraprotonated 5, 7, and 11 exist in one conformation regardless of the solvent. These observations have been attributed to an interaction between DMSO and the pyrrolic N-H protons of the porphyrin cores which is inhibited by metalation (Zn2+) or protonation of the porphyrin moiety. Molecular dynamics calculations reveal that the intracavity interactions of 5 with DMSO are more important than the intercavity interactions which result in discrete, unsymmetrical conformations of the dimer. In contrast, tris[m,m-(methylene(m-pyridinesulfonyl)imino)methylene]-mono((((methyleneoxy) carbonyl)oxy)methylene)-strati-bis(5,10,15,20-tetraphenylporphyrin) (6), tetrakis[m,m-(methylenecyanoimino)-methylene]-strati-bis(5,10,15,20- tetraphenylporphyrin) (8), tris[m,m-(methylenecyanoimino)methylene]-mono((((methyleneoxy)carbonyl)oxy) methylene)-strati-bis(5,10,15,20-tetraphenylporphyrin) (9), and tetrakis[m,m-(methylene(formainido)imino)methylene]-strati-bis(5,10,15,20- tetraphenylporphyrin) (10) do not show any conformational changes upon switching from chloroform to DMSO. This is attributed to the long interplanar distances calculated for the porphyrin dimers which prevent any intracavity coordination of DMSO with both porphyrin moieties. 1H NMR variable-temperature experiments of porphyrin dimer 5 in DMSO show that the conformation of the dimer is greatly affected by temperature. While at room temperature 5 exists in more than one conformation, at higher temperatures (150 °C) only one conformation is populated. It is proposed that at room temperature, the existence of a hydrogen-bonding network between DMSO and the dimer results in more than one conformation, while at higher temperatures the network is destroyed to furnish an average conformation.
Triazole- and triazolium-containing porphyrin-cages for optical anion sensing
Gilday, Lydia C.,White, Nicholas G.,Beer, Paul D.
, p. 7092 - 7097 (2012/07/14)
Triazole and triazolium groups have been integrated into a zinc(ii) metalloporphyrin-based structural framework to produce two porphyrin-cages for anion sensing applications. UV/visible spectroscopic titration investigations reveal both host systems exhibit strong anion binding affinities, with the positively-charged triazolium-porphyrin cage capable of colorimetric sensing halides, fluoride and chloride, and oxoanions in acetone-water solvent mixtures.
Polyporphyrin thin films from the interfacial polymerization of mercaptoporphyrins
Wen, Liqin,Li, Ming,Schlenoff, Joseph B.
, p. 7726 - 7733 (2007/10/03)
Free-standing ultrathin films of aporphyrin homopolymer have been synthesized by interfacial polymerization of a mercaptoporphyrin. Coupling of 5,10,15,20-tetrakis(α-mercapto-p-tolyl)porphyrin at the water/ chloroform interface by copper acetate yields continuous, flexible films after drying with supercritical CO2. These films are amorphous and retain many characteristics of the monomeric porphyrin, such as the property that they may be metalated. Spectroscopic evidence suggests efficient cross-linking of thiols through disulfide coupling occurs in these polyporphyrins to form a network. Polymerization is accompanied by the introduction of carbonyl functionality, probably the transformation of residual thiols to thioacetate by metal-mediated reaction with excess acetate ion. As an example of the catalytic properties of these polymers, they are shown to promote photooxidation of thietane to the corresponding sulfoxide by sensitizing singlet oxygen production.
Synthesis of a Spheroidal Bis-porphyrin: a Ligand Designed to Accept Two Catalytic Metal Ions in an Isolated Environment
Zhang, Hong-Yue,Yu, Jian-Qiu,Bruice, Thomas C.
, p. 11339 - 11362 (2007/10/02)
A spheroidal bis-porphyrin (dual capped quadruply cofacial dimeric tetraphenylporphyrin, 1), designed to be employed as a ligand for a class of catalysts that mimic the combined enzyme activities of superoxide dismutase and catalase, has been synthesized
Syntheses of Quadruply Two- And Three-Atom, Aza-Bridged, Cofacial Bis(5,10,15,20-tetraphenylporphyrins)
Bookser, Brett C.,Bruice, Thomas C.
, p. 4208 - 4218 (2007/10/02)
Several syntheses for quadruply aza-bridged, cofacial bis(5,10,15,20-tetraphenylporphyrins) were investigated. Reaction of 5,10,15,20-tetrakis(α-bromo-m-tolyl)porphyrin (2) with p-toluenesulfonamide or cyanamide and Cs2CO3 at high dilution in dimethylformamide produced the tosyl and cyano dimers 3a and 3b in 8% yield each. The method of choice was the reaction of porphyrin 2 with tosylamido porphyrin 5a under the same conditions to give dimer 3a in 38% yield. Biphenyl radical anion induced desulfonylation of 3a provided the amino dimer 3c (41%). Reaction of porphyrin 2 with tosylamido porphyrin 13 provided the dimer 14 (of reduced bridge length) in 1% yield. Other methods for the synthesis of 3a and 3c are also discussed. UV/vis and 1H NMR spectroscopic results suggest an eclipsed "screwed-down" preferred conformation for these dimers, and molecular models are used to illustrate this conformational possibility. (1) Several terms have been used to describe the orientation of one porphyrin ring parallel and coplanar on top of another (i.e., strati by Kagen,5b face to face by Collman,5a and cofacial by Chang3b). Whereas the term cofacial is now generally the most commonly used descriptor, we prefer the usage of strati (from stratum, Latin for covering) for the specific naming of compounds, since it allows for more detailed structural information than simple letter-number shorthand abreviations. Moreover, a new shorthand naming system will be presented in the body of this account,17 which derives naturally from the strati terminology used in the Experimental Section.
