Rosarin: a new, easily prepared hexapyrrolic expanded porphyrin

Sessler, Jonathan L.; Weghorn, Steven J.; Morishima, Takashi; Rosingana, Miguel; Lynch, Vincent M.; Lee, Virgil

doi:10.1021/ja00047a061

Cited by 116 publications

(80 citation statements)

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“…1 37 , and trihydrochloride salt of 4,9,13,18,22,27-hexaethyl-5,8,14,17,23,26-hexamethyl-2,11,20-triphenylrosarin 38 , abbreviated as triphenylrosarin. Monoprotonated form of sapphyrin 1 and free-base form of sapphyrin 2 were obtained from a CH 2 Cl 2 solution of their dihydrochloride salts by washing with water and 0.5 M Na 2 CO 3 , respectively.…”

Section: Methodsmentioning

confidence: 99%

“…[31][32][33][34][35][36][37][38][39][40] Sapphyrin, a 22π electron aromatic pentapyrrolic expanded porphyrin which uptakes two protons at most, is a good anion receptor for fluoride, phosphate and phenylphosphate. [31][32][33][34][35][36]40 Rubyrin 31,34,37 , a 26π electron aromatic hexapyrrolic macrocycle which uptakes two protons, recognizes chloride and GMP and triphenylrosarin 38 , a fully conjugated 24π electron hexapyrrolic macrocycle which uptakes three protons, also recognizes chloride. Protonated sapphyrin acts as an efficient carrier for the transport of fluoride anion 32 , GMP and AMP 34 in a model three-phase H 2 O-CH 2 Cl 2 -H 2 O bulk liquid membrane system.…”

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confidence: 99%

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Potentiometric Responses of Expanded Porphyrin Incorporated Liquid Membrane Electrodes toward a Series of Inorganic and Organic Anions

et al. 1998

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Much effort has been devoted to developing anion selective electrodes of which selectivity deviates from the Hofmeister series. Since the response mechanism of conventional anion selective electrodes relies on ion exchange, i.e., a charge-charge interaction, their selectivities obey the Hofmeister series. [1][2][3] Simon and coworkers have reported on chloride and nitrite selective electrodes based on neutral trialkyltin derivatives and lipophilic vitamin B 12 derivatives. 4-7 These electrodes were the first anion selective electrodes of which selectivity sequence did not obey the Hofmeister series. Since then, a number of anion-selective liquid membrane electrodes have been developed by using a variety of hosts; metalloporphyrins [8][9][10][11][12][13][14][15][16] , metallocenes 17 , organo-mercury derivatives 18 , diphosphonium dication salts 19,20 , diquarternary ammonium dication salts 21 , bisthiourea derivatives with multitopic recognition sites based on hydrogen bonding 22,23 , guanidinium derivative salts with hydrogen bond acceptor sites 24 , lipophilic macrocyclic polyamines with an electrostatic interaction [25][26][27][28][29] , and cytosine-pendant triamine with a ditopic interaction based on a charge-charge interaction and complementary base pairing. 30 The latter two groups are different from the others because the protonation of the sensory elements at the interface of the membrane is a prerequisite for accommodating the guest anions and yielding their potential responses.Sessler and coworkers recently reported that protonated expanded porphyrins recognize anions through a charge-charge interaction and hydrogen bonding formation. [31][32][33][34][35][36][37][38][39][40] Sapphyrin, a 22π electron aromatic pentapyrrolic expanded porphyrin which uptakes two protons at most, is a good anion receptor for fluoride, phosphate and phenylphosphate. [31][32][33][34][35][36]40 Rubyrin 31,34,37 , a 26π electron aromatic hexapyrrolic macrocycle which uptakes two protons, recognizes chloride and GMP and triphenylrosarin 38 , a fully conjugated 24π electron hexapyrrolic macrocycle which uptakes three protons, also recognizes chloride. The potentiometric responses of liquid membrane electrodes based on expanded porphyrins such as sapphyrin, rubyrin and triphenylrosarin, toward a series of organic carboxylates and inorganic anions were investigated. pH titration of these expanded porphyrin based electrodes with and without a guest anion in the sample solution showed that protonation of the expanded porphyrins at the surface of the electrode membrane is a prerequisite for accommodating the guest anions and yielding their potential responses. The electrodes strongly responded to benzoates, but rather less to inorganic anions and saturated aliphatic organic carboxylates. The selectivity sequences for the sapphyrin based electrode were found in some cases to deviate from the Hofmeister series; fluoride preference over chloride and bromide is particularly noted. Interesting responses were observed by the electrodes fo...

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Potentiometric Responses of Expanded Porphyrin Incorporated Liquid Membrane Electrodes toward a Series of Inorganic and Organic Anions

et al. 1998

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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%

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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“…Although a large number of 'expanded porphyrins' (for comprehensive reviews of expanded porphyrins see Refs 1-3) are now known, the number of Hückel (4n 2) non-aromatic systems containing a bipyrrole subunit is limited [4][5][6][7][8][9]. Given that systems derived from bipyrrole units can function as potential anion and/or neutral substrate receptors, we have devoted effort of late to the synthesis of new macrocycles whose framework contains one or more bipyrroles [4][5][6][7].…”

Section: Introductionmentioning

confidence: 99%

“…Given that systems derived from bipyrrole units can function as potential anion and/or neutral substrate receptors, we have devoted effort of late to the synthesis of new macrocycles whose framework contains one or more bipyrroles [4][5][6][7]. In this paper we report the synthesis and structural characterization of the macrocycle [1ÁH 2 O], a derivative of a new class of tetrapyrrolic expanded porphyrins [10,11].…”

Section: Introductionmentioning

confidence: 99%

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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Rosarin: a new, easily prepared hexapyrrolic expanded porphyrin

Cited by 116 publications

References 0 publications

Potentiometric Responses of Expanded Porphyrin Incorporated Liquid Membrane Electrodes toward a Series of Inorganic and Organic Anions

Potentiometric Responses of Expanded Porphyrin Incorporated Liquid Membrane Electrodes toward a Series of Inorganic and Organic Anions

Expanded porphyrins. Synthetic materials with potential medical utility

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

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