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dc.contributor.authorMisra, R-
dc.contributor.authorKumar, R-
dc.contributor.authorChandrashekar, T K-
dc.contributor.authorSuresh, C H-
dc.contributor.authorNag, A-
dc.contributor.authorGoswami, D-
dc.date.accessioned2014-05-13T09:20:32Z-
dc.date.available2014-05-13T09:20:32Z-
dc.date.issued2006-
dc.identifier.citationJournal of the American Chemical Society 128(50):16083-16091;20 Dec 2006en_US
dc.identifier.issn0002-7863-
dc.identifier.urihttp://ir.niist.res.in:8080/jspui/handle/123456789/1407-
dc.description.abstractSyntheses, spectroscopic, electrochemical, and third-order nonlinear optical susceptibilities of a series of 22 pi smaragdyrins and their corresponding Rh(I) derivatives bearing phenylacetylene substituents and ferrocene-containing substituents are reported. The synthetic strategy involved a [3+2] acid-catalyzed oxidative coupling reaction of the appropriate dipyrromethane and oxatripyrrane. The desired meso substituents, such as phenylacetylenylphenyl and the ferrocenes, were incorporated to the dipyrromethane unit prior to the oxidative coupling reaction. The optical absorption, emission characteristics, and the quantum yield of the smaragdyrin conjugates depends on the nature of the substituent, nature of linker group, and the spacer length. Theoretical studies at the DFT level suggest high delocalization of electrons confined to only four of the five available heterocyclic rings for the free bases. However, upon Rh(I) metalation, the pi-electron delocalization is extended to all the heterocyclic rings. The two-photon absorption cross section (TPA) values sigma((2)) measured through the open aperture Z-scan method, increases linearly with enhanced pi-electron delocalization for the smaragdyrins containing phenylacetylene substituents. The meta branching of substituents decreases sigma((2)) values. Introduction of Rh(I) to the smaragdyrin cavity enhances the sigma((2)) values by about 3-10 orders of magnitude, attributed to the increased aromatic character upon Rh(I) insertion. The calculated molecular electrostatic potential (MESP) and harmonic oscillator model of aromaticity (HOMA) for the free bases and the Rh( I) derivatives justifies such a conclusion. A linear correlation observed for the second oxidation potential of Rh(I) derivatives and corresponding free bases also support the increased aromaticity upon Rh(I) insertion. The electrochemical data for ferrocene-containing smaragdyrins reveal easier ring oxidation by about 50-130 mV and harder ferrocene oxidation by 40180 mV suggesting electron-donating nature of the ferrocene upon linking with the smaragdyrin pi system. The TPA cross section value of 88782 GM observed for 5g represents one of the highest values known for a metalloexpanded porphyrin derivative.en_US
dc.language.isoenen_US
dc.publisherAmerican Chemical Societyen_US
dc.subjectModified expanded porphyrinsen_US
dc.subjectStrong 2-Photon absorptionen_US
dc.subjectMesoen_US
dc.subjectChromophoresen_US
dc.subjectCorroleen_US
dc.subjectDimersen_US
dc.title22 pi smaragdyrin molecular conjugates with aromatic phenylacetylenes and ferrocenes: Syntheses, electrochemical, and photonic propertiesen_US
dc.typeArticleen_US
Appears in Collections:2006

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