Turcasarin, the Largest Expanded Porphyrin to Date

Sessler, Jonathan L.; Weghorn, Steven J.; Lynch, Vincent M.; Johnson, Martin R.

doi:10.1002/anie.199415091

Cited by 173 publications

(121 citation statements)

References 31 publications

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“…In fact, such examples of neutral substrate complexation with an expanded porphyrin are not numerous [7,26]. Unfortunately, preliminary tests with 1, conducted using 1 H NMR analyses in either CD 2 Cl 2 or DMSO-d 6 and using substrates such as chloride and fluoride (tetrabutylammonium salts) as well as neutral substrates such as methanol and catechol, reveal that, at least, this prototypic system is not effective in this regard. On the other hand, preliminary studies reveal that it is able to coordinate the uranyl cation and complex BF 2 ; further studies of 1 as a metal-coordinating ligand are ongoing.…”

Section: Discussionmentioning

confidence: 98%

Synthesis and Characterization of New Non-aromatic Texaphyrin-type Expanded Porphyrins

Meyer

Hoehner

Lynch

et al. 1999

J. Porphyrins Phthalocyanines

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The synthesis and X-ray diffraction-based characterization of a texaphyrin-type non-aromatic expanded porphyrin, 13,18,22,27-tetraethyl-14,17,23,26-tetramethyl-20-p-nitrophenyl-3,10,28,29,30,31-hexaazahexacyclo[23.2.1.04,9.112,15.116,19.121,24]untriaconta-2, 4, 5, 7, 10,12,14,16,18,-20,22,24(30),25,27-tetradecaene (1), is reported. This Schiff base macrocycle was prepared in good yield via the 1:1 HCl -catalyzed condensation of a tetrapyrrole dialdehyde precursor, (di(5-formyl-4,4'-diethyl-3,3'-dimethyl-2,2'-bipyrrole)-p-nitrophenylmethine), with 1,2-phenylenediamine. Compound 1 was assigned as being a 26 π-electron non-aromatic benzannulene on the basis of both proton NMR and single-crystal X-ray diffraction analyses. The latter studies, in particular, revealed a non-planar macrocyclic structure co-crystallized with a molecule of water. By varying either the diamine used in the cyclization step and/or the substituent in the meso-position of the tetrapyrrolic precursor, a range of other systems analogous to 1 could be obtained. The resulting systems were found to present good stability both in the solid state and in solution.

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Section: Discussionmentioning

confidence: 98%

Synthesis and Characterization of New Non-aromatic Texaphyrin-type Expanded Porphyrins

Meyer

Hoehner

Lynch

et al. 1999

J. Porphyrins Phthalocyanines

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“…Asian J. 2017,12,[6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] Introducing as teric block into the macrocyclic cavity is another strategy for retaining ap lanar configuration. This approach was previouslye xplored by Osuka and co-workers to maintain ap lanar macrocycle (30), but it fell short of ac ompletely conjugated system.…”

Section: Core-modified Octaphyrinsmentioning

confidence: 99%

“…Asian J. 2017,12,[6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] www.chemasianj.org distinctly different, because one of them is complexed by two carbon and nitrogen atoms (NNCC core), whereas the other binds through one carbon atom and three nitrogena toms (NNNC core). Of particulari nterest is the modified topology from Hückel antiaromaticity to Mobiusa romaticityf or the 36 p-conjugated pathway.…”

Section: Metal Complexesmentioning

confidence: 99%

“To Twist or Not to Twist”: Figure‐of‐Eight and Planar Structures of Octaphyrins

Shivran

Gadekar

Anand

2016

Chemistry An Asian Journal

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Amongst the various porphyrinoids, octaphyrin has attracted significant attention owing to its diverse syntheses, conformations, and metal-ligationp roperties. Octaphyrin is ah igher homologue of porphyrin and is formed by linking together heterocycles such as pyrrole, furan, thiophene, ands elenophene through a-a or a-meso carbon bonds. The planar conformation is mainly achievedt hrough inversion of the heterocyclic units from the center of macrocycle;a voiding meso-bridges;introducing a para-quinodimethane bridge;e mployinganeo-confusion approach; protonation;a nd by generating dianionics pecies. In this Focus Review,r ecent synthetic advancements in the field of octaphyrins are summarized.T he twisted conformation of the octaphyrinb inds to two metal ions in at etracoordinate geometry.T he diphosphorus complex of octaphyrin represents the first example of as table expanded isophlorin.

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“…For instance, systems as diverse as rubyrin [28], rosarin [29], amethyrin [30], and turcasarin [31] have been shown, when protonated, to bind anions in the solid state. The protonated forms of other more newly prepared systems, including the previously unknown heptaphyrin and octaphyrin derivatives 10 and 11, constructed via a noval oxidative ring closure procedure, also appear to bind appropriately sized anionic substrates within their central cores.…”

Section: Expanded Porphyrinsðpotential Medical Utilitymentioning

confidence: 99%

“…The ®rst hint, at least for us, that expanded porphyrins need not be planar came with the synthesis and structural characterization of turcasarin [31]. This system was found to adopt a ®gure-eight conformation both in solution and in the solid state, as do several other recently-prepared expanded porphyrin systems [1].…”

Section: Towards the Future The Generation Of 3-dimensional Systemsmentioning

confidence: 99%

Expanded porphyrins. Synthetic materials with potential medical utility

Sessler¹,

Tvermoes²,

Davis³

et al. 1999

Pure and Applied Chemistry

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A number of aromatic and nonaromatic expanded porphyrins have been prepared in the authors' laboratories. These are allowing a number of important themes to be explored, including the construction of novel cation-and anion-complexing agents and the generation of drug candidates with considerable therapeutic potential. In this paper, the use of gadolinium(III) and lutetium(III) texaphyrin derivatives as, respectively, adjuvants for X-ray radiation cancer therapy and photosensitizers for use in photodynamic treatments of cancer, atheromatous plaque, and age-related macular degeneration will be reviewed. Also discussed are the use of water soluble sapphyrins as potential¯uorescent phosphate sensors and organic soluble 2,3-dipyrrylquinoxaline derivatives as possible¯uoride anion signaling agents. Recent synthetic work, designed to produce expanded porphyrins with new shapes and novel topologies, is also summarized.

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Turcasarin, the Largest Expanded Porphyrin to Date

Cited by 173 publications

References 31 publications

Synthesis and Characterization of New Non-aromatic Texaphyrin-type Expanded Porphyrins

Synthesis and Characterization of New Non-aromatic Texaphyrin-type Expanded Porphyrins

“To Twist or Not to Twist”: Figure‐of‐Eight and Planar Structures of Octaphyrins

Expanded porphyrins. Synthetic materials with potential medical utility

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