34π Octaphyrin:  First Structural Characterization of a Planar, Aromatic [1.0.1.0.1.0.1.0] Octaphyrin with Inverted Heterocyclic Rings

Anand, Venkataramanarao G.; Pushpan, Simi K.; Venkatraman, Sundararaman; Dey, Abhishek; Chandrashekar, Tavarekere K.; Joshi, Bhavani S.; Roy, Raja; Teng, Weijie; Senge, Karin Ruhlandt

doi:10.1021/ja011265w

Cited by 68 publications

(59 citation statements)

References 11 publications

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“…As discussed briefly in Section 5.1, Furuta and co-workers recently reported the synthesis of a variety of meso-arylsubstituted expanded porphyrins obtained from a modified Rothemund condensation of pyrrole and pentafluorobenzaldehyde. [93] These researchers obtained porphyrin (11-12 %), N-fused pentaphyrin 78 (14-15 %), hexaphyrin 79 (16-20 %), heptaphyrin (4-5 %), octaphyrin 120 (5-6 %), nonaphyrin 121 (2-3 %), as well as several higher homologues in very low yield by condensation of both precursors at relatively high [116] concentration (that is, 67 mm in both reactants in CH 2 Cl 2 ) in the presence of 4.2 mm BF 3 ·Et 2 O, followed by oxidation with DDQ.…”

Section: Figure-eight Tetrathiaoctaphyrin and Dihydrotetrathiaoctaphyrinmentioning

confidence: 98%

“…These macrocycles were found to be planar, presumably as a consequence of having two b-unsubstituted thiophene or selenophene subunits inverted. [116] The synthesis of 119 a and 119 b is summarized in Scheme 37. It involves the oxidative coupling of the linear heterotetrapyrrolic precursors 106 a and 106 e, and gives rise to 119 a and 119 b, respectively, both of which were isolated in 5 % yield.…”

Section: Figure-eight Tetrathiaoctaphyrin and Dihydrotetrathiaoctaphyrinmentioning

confidence: 99%

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Synthetic Expanded Porphyrin Chemistry

2003

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Expanded porphyrins are synthetic analogues of the porphyrins, and differ from these and other naturally occurring tetrapyrrolic macrocycles by containing a larger central core with a minimum of 17 atoms, while retaining the extended conjugation features that are a hallmark of these quintessential biological pigments. The result of core expansion is to produce systems with novel spectral and electronic features, interesting and, often unprecedented, cation-coordination properties, and, in many cases, an ability to bind anions in certain protonation states. Also adding to the appeal of expanded porphyrins is their central role in addressing issues of aromaticity. In many cases, they also display structural features, such as decidedly nonplanar "figure-eight" motifs, that have no antecedents in the chemistry of porphyrins or related macrocyclic compounds. In this Review, the various synthetic approaches now being employed to produce expanded porphyrins as well as their various applications-related aspects are discussed.

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Section: Figure-eight Tetrathiaoctaphyrin and Dihydrotetrathiaoctaphyrinmentioning

confidence: 98%

Section: Figure-eight Tetrathiaoctaphyrin and Dihydrotetrathiaoctaphyrinmentioning

confidence: 99%

Synthetic Expanded Porphyrin Chemistry

2003

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“…Aj udiciousc hoice of precursor has allowed the development of procedures that can control the number of meso-carbonb ridgesi nag iven octaphyrina nd, hence,i ts topology.T his control is very much exemplified by ( 43). [31] Under modified reactionc onditions, it was subjected to an acid-catalyzed condensation with an aryl aldehyde to yield 34 p octaphyrin 46 (Scheme18). [34] Despite the presence of two additional meso-carbon atoms in the framework of macrocycle 43,o ctaphyrin 46 still retained a3 4 p electron motif.…”

Section: Core-modified Octaphyrinsmentioning

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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“…Chandrashekar and co-workers have synthesized several core-modified expanded porphyrins such as sapphyrins, [3] smaragdyrins, [4] rubyrins, [5] hexaphyrins, [6] heptaphyrins, [7] and octaphyrins [8] and showed that some of these systems can be used as ligands for metal ions and receptors for anions. Although several expanded porphyrins, both aza and core-modified analogues, have been synthesized and demonstrated to have tremendous potential in various ap-5390 macrocycles in the dyads interact weakly with each other and maintain their independent characteristic features.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Mono‐Functionalized Core‐Modified Expanded Porphyrin Building Blocks and Covalently Linked Expanded Porphyrin Dyads

Pareek

Ravikanth

2011

Eur J Org Chem

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A series of mono-functionalized core-modified expanded porphyrin building blocks such as thiasapphyrin, thiarubyrin, oxasmaragdyrin, and BF 2 -oxasmaragdyrin have been synthesized by simple condensation of readily available precursors. The mono-functionalized core-modified expanded porphyrin building blocks were used to synthesize the first three examples of covalently linked diphenylethyne-bridged dyads containing two different expanded porphyrin macrocycles, namely thaisapphyrin-BF 2 -oxasmaragdyrin, thiarubyrin-BF 2 -oxasmaragdyrin, and thiasapphyrin-thiarubyrin, by coupling appropriate mono-functionalized expanded porphyrin building blocks under mild Pd 0 coupling reaction conditions. The three dyads were freely soluble in common organic solvents and characterized by MS, NMR, absorption, electrochemical, and fluorescence techniques. The NMR, absorption, and electrochemical studies indicated that the two

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34π Octaphyrin: First Structural Characterization of a Planar, Aromatic [1.0.1.0.1.0.1.0] Octaphyrin with Inverted Heterocyclic Rings

Cited by 68 publications

References 11 publications

Synthetic Expanded Porphyrin Chemistry

Synthetic Expanded Porphyrin Chemistry

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

Synthesis of Mono‐Functionalized Core‐Modified Expanded Porphyrin Building Blocks and Covalently Linked Expanded Porphyrin Dyads

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